Method of fixing and bleach-fixing a silver halide photographic material using mesoionic compounds

ABSTRACT

A process for processing an imagewise exposed silver halide photographic material comprising a support having thereon at least one light-sensitive silver halide emulsion layer, comprising the steps of developing in a developing bath and processing in a bath having a fixing ability, wherein the bath having the fixing ability contains at least one mesoionic compound represented by formula (I): ##STR1## In a second embodiment, a process is disclosed for processing an imagewise exposed silver halide color photographic material comprising a support having thereon at least one light-sensitive silver halide emulsion layer, comprising the steps of subjecting the material to color development, and then subjecting the material to blix in a blix bath, wherein the blix bath contains at least one mesoionic compound represented formula (III) or (IV): ##STR2##

TECHNICAL FIELD

The present invention relates to a process and composition for theprocessing of a silver halide photographic material. More particularly,the present invention relates to a process for processing a silverhalide photographic material which provides excellent desilveringproperties and a processing composition therefor. Further, the presentinvention relates to a process for processing a silver halidephotographic material which is little subject to thermostain on thematerial after processing and provides excellent desilvering propertiesand a processing composition therefor.

Moreover, the present invention relates to a process for processing asilver halide color photographic material which is little subject tobleach fogging caused by blix and provides an excellent solutionstability and a processing composition therefor.

BACKGROUND ART

In general, the processing of a silver halide color photographicmaterial consists of steps of color development and desilvering. Silverwhich has been produced in the development step is then oxidized with ableaching agent and dissolved with a fixing agent. As bleaching agentthere may be mainly used a, ferric complex salt, e.g.,aminopolycarboxylic acid-ferric complex salt. As fixing agent there maybe normally used a thiosulfate.

On the other hand, the processing of a black-and-white photographiclight-sensitive material consists of steps of development and removal ofunexposed silver halide. Unlike the processing of a color photographiclight-sensitive material, the black-and-white photographiclight-sensitive material which has been developed is then fixed withoutbeing bleached. In this case, too, as fixing agent there is normallyused a thiosulfate.

It has been desired to speed up both the color development and theblack-and-white development. It has thus been studied to shorten eachprocessing step. This doesn't except the fixing step. Various fixingaccelerators have been studied. Little or no effective fixingaccelerators have been found. It is possible to use fixing agents otherthan thiosulfates to-speed up the fixing step.

Examples of fixing agents to replace thiosulfates include1,2,4-triazolium-3-thiolates of mesoionic compounds as described in U.S.Pat. No. 4,378,424, and JP-A-57-150842 (the term "JP-A" as used hereinmeans an "unexamined published Japanese patent application"). However,no full studies have been made on these fixing agents.

JP-A-1-201659 discloses the use of mesoionic compounds as bleachaccelerators in the bleaching bath or blix bath. Further, JP-A-2-44355discloses the use of 1,2,4-triazolium-3-thiolate compounds as fixingaccelerators in the fixing bath. However, the above cited patents giveno reference to the effects of the present invention.

Other examples of mesoionic compounds include those disclosed in U.S.Pat. Nos. 4,003,910, 4,675,276, 4,624,913, and 4,631,253, andJP-A-62-217237, JP-A-64-3641, JP-A-60-144737, JP-A-62-253161,JP-A-62-287239, JP-A-61-176920, JP-A-62-96423, and JP-A-1-154056.However, all these mesoionic compounds are intended to be incorporatedin the photographic light-sensitive material or the developer. The abovecited patents give no reference to the effects of the present invention.

There is an increasing demand for the improvement in the imagepreservability. For this purpose, studies have been made on both thematerial to be used in the light-sensitive material and the finalprocessing bath. However, these approaches still leave much to bedesired. Thus, there have been not yet attained desired desilveringproperties and image preservability. It has thus been desired todrastically improve these properties.

Further, the above mentioned bleaching agent and fixing agent are usedin the same bath as blix bath in the processing of a color photographicpaper, etc., for the purpose of speeding up the processing. Thebleaching agent to be used in the blix bath is normally anethylenediaminetetraacetic acid-ferric complex salt. It is the recenttendency that an oxidizing agent having a higher oxidizing power (highredox potential) is used in the bleaching bath to further speed up theprocessing. However, it has been known that such an oxidizing agentcauses significant bleach fogging or that if used as blix bath, itcauses a problem of solution stability or the like. The solutionstability problem is that the thiosulfate is deteriorated by oxidationand then precipitated.

In recent years, this problem has become more remarkable as thereplenishment rate decreases. In order to inhibit the oxidation ofthiosulates, sulfites are normally used as preservatives. However, ifsulfites are used in a large amount, they are oxidized to causeprecipitation of Glauber's salt or other problems. Thus, it is difficultto use sulfites as a countermeasure.

On the other hand, U.S. Pat. No. 4,378,424, and JP-A-57-150842 disclosethat as fixing agents to replace thiosulfates there may be usedmesoionic compounds. However, the above cited patents give no referenceto the effects in the blix bath as stated herein.

Moreover, JP-A-2-44355 discloses the incorporation of1,2,4-triazolium-3-thiolate compounds as fixing accelerators in thefixing bath. JP-A-1-201659 discloses the incorporation of mesoioniccompounds as bleach accelerators in the bleach or blix bath. However,the above cited patents give reference neither to the use of mesoioniccompounds as fixing agents in the blix bath nor to the effects of thepresent invention.

If these mesoionic compounds are used as accelerators, they often workwell in a small amount. These mesoionic compounds serve to removesubstances which are adsorbed by silver halide (or silver). Thus, theseapproaches greatly differ in the amount of mesoinic compounds to be usedand their functions from the present invention, in which mesoioniccompounds are used as fixing agents. Therefore, the present inventioncannot be easily worked out from the above cited patents.

Further examples of mesoionic compounds are disclosed in U.S. Pat. Nos.4,003,910, 4,675,276, 4,624,913, and 4,631,253, and JP-A-62-217237,JP-A-64-3641, JP-A-60-144737, JP-A-62-253161, JP-A-62-287239,JP-A-61-176920, JP-A-62-96943, and JP-A-1-154056. However, all thesemesoionic compounds are intended to be incorporated in the photographiclight-sensitive material or the developer. The above cited patents giveno reference to the effects of the present invention.

Thus, it can be said that there have been not yet found a blix bath thatcan eliminate both the bleach fogging problem and the solution stabilityproblem at the same time.

DISCLOSURE OF THE INVENTION

It is therefore a first object of the present invention to provide aprocess for processing a silver halide photographic material whichprovides excellent desilvering properties and is little subject tothermostain after processing.

It is a second object of the present invention to provide a process forprocessing a silver halide photographic material by using a blix bathwhich is little subject to bleach fogging and provides an excellentsolution stability.

These and other objects of the present invention will become moreapparent from the following detailed description and examples.

The first object of the present invention is accomplished by a processfor processing a silver halide photographic material which comprisesprocessing an exposed silver halide photographic material comprising asupport having thereon at least one light-sensitive silver halideemulsion layer, wherein a bath having a fixing ability contains at leastone mesoionic compound represented by the general formula (I): ##STR3##wherein X represents N or C--R₁ ; Y and Z each represents O, S, N, N--R₂or C--R₃ ; U represents O, S or N--R₄ ; and A.sup.⊖ represents--O.sup.⊖, --S.sup.⊖ or --N.sup.⊖ R in which R₁, R₂, R₃ and R₄ may bethe same or different and each represents --T)_(n) R' (wherein Trepresents --S--, --O--, --N(R")--, ##STR4## --C(═S)--, --SO₂ -- orcombination thereof; and n represents an integer 0 or 1); R, R' and R"may be the same or different and each represents a hydrogen atom, analkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group or aheterocyclic group, with the proviso that at least one of R, R' and R"is substituted by carboxylic acid or sulfonic acid group; and X and U, Yand Z, and Z and U may be ring-closed (This process will be hereinafterreferred to as "first embodiment of the present invention").

In the first embodiment of the present invention, examples of the "bathhaving a fixing ability" include fixing bath and blix bath.

The second object of the present invention is accomplished with aprocess for processing a silver halide color photographic material,characterized in that the blix bath contains at least one mesoioniccompound as fixing agent and is substantially free of other fixingagents (This process will be hereinafter referred to as "secondembodiment of the present invention").

The present invention will be further described hereinafter.

The mesoionic compounds to be used in the present invention are compoundgroups defined in W. Baker and W. D. Ollis, "Quarterly Review", 11, 15(1957) and "Advances in Heterocyclic Chemistry", 19, 1 (1976). Thesemesoionic compounds represent 5- or 6-membered heterocyclic compoundswhich cannot be satisfactorily represented by only one covalentstructural formula or polar structural formula and have a sextet ofπ-electrons related to all the atoms constituting the ring, the ringbeing partially positively charged to balance an equal negative chargeon atoms or atomic groups outside the ring.

The mesoionic compound represented by the general formula (I) to be usedin the bath having a fixing ability used in the first embodiment of thepresent invention will be further described hereinafter.

In the general formula (I), X represents N or C--R₁. Y and Z eachrepresents O, S, N, N--R₂ or C--R₃. U represents O, S or N--R₄. Examplesof a heterocyclic group formed of a combination of X, Y, Z and U includeimidazoliums, pyrazoliums, oxazoliums, thiazoliums, triazoliums,tetrazoliums, thiadiazoliums, oxadiazoliums, thiatriazoliums, andoxatriazoliums.

A.sup.⊖ represents --O.sup.⊖, --S.sup.⊖ or --N.sup.⊖ R.

R₁, R₂, R₃ and R₄ may be the same or different and each represents--T)_(n) R' (wherein T represents --S--, --O--, ##STR5## --SO₂ -- or agroup formed of an arbitrary combination thereof (e.g., carbamoyl,ureide, thiocarbamoyl, thioureide, sulfamoyl, carbonamide, sulfonamide).The suffix n represents 0 or 1.

R, R' and R" may be the same or different and each represents a hydrogenatom, a substituted or unsubstituted C₁₋₆ alkyl group (e.g., methyl,ethyl, n-propyl, n-butyl, t-butyl, n-hexyl, hydroxyethyl,dimethylaminoethyl, cyanoethyl, carboxyethyl, carboxymethyl,carboxypropyl, 1,2-dicarboxyethyl, sulfoethyl, sulfopropyl, sulfobutyl,2-hydroxy-3-sulfopropyl), a substituted or unsubstituted C₃₋₁₀cycloalkyl group (e.g., cyclopropyl, cyclobutyl, cyclohexyl,4-hydroxycyclohexyl, 4-carboxycyclohexyl, 4-sulfocyclohexyl), asubstituted or unsubstituted C₂₋₈ alkenyl group (e.g., vinyl, propenyl,4-carboxy-2-butenyl), a substituted or unsubstituted C₂₋₈ alkynyl group(e.g., propargyl) or a substituted or unsubstituted C₁₋₈ heterocyclicgroup (e.g., 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-thienyl, 1 -pyrazolyl,1-imidazolyl, 2-tetrahydrofuryl), with the proviso that at least one ofR, R' and R" is substituted by carboxylic acid or salt thereof (e.g.,sodium salt, potassium salt, ammonium salt) or sulfonic acid or saltthereof (e.g., sodium salt, potassium salt, ammonium salt).

X and U, Y and Z, and Z and U may be ring-closed.

If R, R' and R" contain substituents other than carboxylic acid andsulfonic acid, examples of such substituents include nitro group,halogen atom (e.g., chlorine, bromine), mercapto group, cyano group,alkyl group (e.g., methyl, ethyl, methoxyethyl), alkoxy group (e.g.,methoxy, ethoxy, methoxyethoxy, methylthioethoxy), alkylthio group(e.g., methylthio, dimethylaminoethylthio, methoxyethylthio), sulfonylgroup (e.g., methanesulfonyl), carbamoyl group (e.g., unsubstitutedcarbamoyl, dimethylcarbamoyl), sulfamoyl group (e.g., unsubstitutedsulfamoyl, methylsulfamoyl), carbonamide group (e.g., acetamide),sulfonamide group (e.g., methanesulfonamide), acyloxy group (e.g.,acetyloxy), sulfonyloxy group (e.g., methanesulfonyloxy), ureide group(e.g., unsubstituted ureide, methylureide), thioureide group (e.g.,unsubstituted thioureide), amino group (e.g., unsubstituted amino,dimethylamino), and hydroxy group.

The compound represented by the general formula (I) may form a salt(e.g., acetate, nitrate, salicylate, hydrochloride, iodate, bromate).

In the general formula (I), A.sup.⊖ preferably represents --S.sup.⊖ --.X preferably represents N or C--R₁. Y preferably represents O, S, N orN--R₂. Z preferably represents N, N--R₂ or C--R₃. U preferablyrepresents N--R₄. When n is 1, T preferably represents ##STR6## or acombination thereof. R' and R" preferably each represents a hydrogenatom or alkyl group. At least one (preferably 1 or 2) of R' and R" ispreferably an alkyl group substituted by carboxylic acid group orsulfonic acid group.

Preferred among compounds represented by the general formula (I) arethose represented by the general formula (II): ##STR7##

In the general formula (II), X' represents N or C--R₅. Y' represents O,S, N--R₆ or ##STR8## R₅, R₆, R₇, R₈, R₉ and R₁₀ may be the same ordifferent and each represents a substituted or unsubstituted C₁₋₆ alkylgroup. R₅, R₇, R₈ and R₉ each may be a hydrogen atom. It is providedthat at least one alkyl group of R₅, R₆, R₇, R₈, R₉ and R₁₀ issubstituted by at least one carboxylic acid group or sulfonic acidgroup.

Specific examples of the compound of the present invention will be setforth below, but the present invention should not be construed as beinglimited thereto. ##STR9##

The synthesis of the compound represented by the general formula (I) or(II) can be accomplished by any suitable method as described in "Journalof Heterocyclic Chemistry" 2, 105 (1965) , "Journal of OrganicChemistry" 32, 2245 (1967), "Journal of Chemical Society" 3799 (1969) ,"Journal of American Chemical Society", 80, 1895 (1958), "ChemicalCommunication", 1222 (1971), "Tetrahedron Letters" 2939 (1972),JP-A-60-87322, "Berichte der Deutschen Chemischen Gesellschaft" 38, 4049(1905), "Journal of Chemical Society Chemical Communication", 1224(1971), JP-A-60-122936, JP-A-60-117240, "Advances in HeterocyclicChemistry", 19, 1 (1976), "Tetrahedron Letters" 5881, (1968), "Journalof Heterocyclic Chemistry", 5, 277 (1968), "Journal of Chemical Society,Parkin Transaction I" , 627 (1974), "Tetrahedron Letters" 1809 (1967)and 1578 (1971), "Journal of Chemical Society", 899 (1935) and 2865(1959), and "Journal of Organic Chemistry" 30, 567 (1965). Examples ofsynthesis of typical compounds of the present invention will bedescribed hereinafter.

SYNTHESIS EXAMPLE 1 Synthesis of Exemplary Compound 1 (1) Synthesis of2-Methoxycarbonylethylisothiocyanate

1,256 ml of triethylamine was added to a solution of 603.6 g ofβ-alaninemethylester sulfate in 1.5 liter of methyl alcohol undercooling with ice. 235 ml of carbon disulfide was added dropwise to thesystem at a temperature of 10° C. or lower. After the dropwise addition,the system was then stirred at a temperature of 10° C. or lower for 1hour. 288 ml of ethyl chloroformate was added dropwise to the system ata temperature of 5° C. or lower. The system was then stirred for 2hours. After the reaction, the reaction solution was then subjected toseparation with ethyl acetate and water. The ethyl acetate phase thusextracted was dried with magnesium sulfate, and then filtered off. Ethylacetate was then distilled off from the system under reduced pressure toobtain 389.1 g (yield: 89.3%) of the desired substance in the form ofoil.

(2) Synthesis of1-Acetyl-1-methyl-4-methoxycarbonylethylthiosemicarbazide

A solution of 101.6 g of 2-methoxycarbonylethylisothiocyanate obtainedin (1) and 61.7 g of 1-acetyl-1-methylhydrazine in 150 ml of methylalcohol was heated under reflux for 2 hours. Methyl alcohol was thendistilled off from the system under reduced pressure. 500 ml of ethylacetate was added to the residue. The resulting crystal was filtered offto obtain 105.0 g (yield: 64.3%) of the desired compound.

(3) Synthesis ofMesoion-1,5-dimethyl-4-methoxycarbonylethyl-1,2,4-triazolium-3-thiolate

300 ml of methyl alcohol and 10 ml of a 28% methyl alcohol solution ofsodium methoxide were added to 93.3 g of1-acetyl-1-methyl-4-methoxycarbonylethylthiosemicarbazide obtained in(2). The system was then stirred at room temperature for 2 hours. Theresulting crystal was filtered off to obtain 67.2 g (yield: 78.0%) ofthe desired compound. m.p. 139°-140° C.

(4) Synthesis ofMesoion-4-carboxyethyl-l,5-dimethyl-1,2,4-triazolium-3-thiolate

64.6 g ofmesoion-1,5-dimethyl-4-methoxycarbonylethyl-1,2,4-triazolium-3-thiolatewas dissolved in 300 ml of water. 100 ml of 5N sodium hydroxide solutionwas added to the system. The system was then heated to a temperature of30° C. with stirring for 2 hours. After the reaction, the system wasneutralized with 45 ml of concentrated hydrochloric acid. The system wasdried under reduced pressure. The resulting residue was recrystallizedfrom 100 ml of water to obtain 49.3 g (yield: 81.6%) of the desiredcompound (m.p. 214°-215° C.). The compound was confirmed to be thedesired compound by NMR, IR, mass spectrum, and elemental analysis.

SYNTHESIS EXAMPLE 2 Synthesis of Exemplary Compound 2 (1) Synthesis ofSodium 1-acetyl-1-methyl-4-sulfoethylthiosemicarbazide

175.3 g of sodium sulfoethylisothiocyanate was added to a solutionobtained by adding 600 ml of methyl alcohol and 300 ml of water to 114.2g of 1-acetyl-1-methylhydrazine. The system was then heated under refluxfor 4 hours. After the reaction, the reaction solution was dried underreduced pressure. The resulting solid matter was then recrystallizedfrom 1 l of methyl alcohol to obtain 169.4 g (yield: 66.0%) of thedesired compound. m.p. 255°-256° C.

(2) Synthesis of sodiummesoion-1,5-dimethyl-4-sulfoethyl-1,2,4-triazolium-3-thiolate

850 ml of methyl alcohol and 5 ml of a 28% methyl alcohol solution ofsodium methoxide were added to 139.8 g of sodium1-acetyl-1-methyl-4-sulfoethylthiosemicarbazide. The system was thenheated under reflux for 3 hours. The system was then cooled to roomtemperature. The resulting crystal was filtered off, and thenrecrystallized from 2 l of a 9:1 mixture of methyl alcohol and water toobtain 99.3 g (yield: 67.9%). m.p. 300° C. or higher

The compound thus obtained was confirmed to be the desired compound byNMR, IR, mass spectrum, and elementary analysis.

SYNTHESIS EXAMPLE 3 Synthesis of Exemplary Compound 52

Mesoion-4-carboxymethyl-1-methyl-l,2,4-triazolium-3-thiolate wasprepared as the desired compound frommethoxycarbonylmethylisothiocyanate obtained in the same manner as inSynthesis Example 1-(1) and 1-formyl-1-methylhydrazine in the samemanner as in Synthesis Example 1. m.p. 231°-232° C.

The suitable amount of the compound of the present invention to beincorporated in the fixing bath or blix bath is in the range of 1×10⁻⁵to 10 mol/l, preferably 1×10⁻³ to 3 mol/l.

If the halogen composition of the silver halide emulsion to beincorporated in the light-sensitive material to be processed is AgBrI(I≧2 mol %), it is preferably used in an amount of 0.5 to 2 mol/l. Ifthe halogen composition is AgBr, AgBrCl or high silver chloride content(AgCl≧80 mol %), it is preferably used in an amount of 0.1 to 1 mol/l.Mesoionic compounds other than those of the present invention can beused in combination with those of the present invention.

Mesoionic compounds of the present invention can be used in combinationwith thiosulfates as described later. However, it is preferred in viewof inhibition of sulfurization that the compound of the presentinvention be used as fixing agent and the processing bath besubstantially free of commonly used thiosulates.

The present inventors made studies on fixing agents other thanthiosulfates to improve the fixing ability. In particular, extensivestudies were made on mesoionic compounds. As a result, it was found thatmesoionic compounds containing water-soluble groups as substituents canprovide a great improvement in the fixing ability. These mesoioniccompounds containing water-soluble substituents exhibited excellentresults in the inhibition of thermostain as those free of water-solublesubstituents. It was an unexpected fact that the presence ofsubstituents in the fixing agent can provide improvements not only indesilvering properties but also in thermostain after processing.

The reason for these phenomena is probably that the incorporation ofwater-soluble substituents prevents a silver complex produced duringfixing from being left in the film. However, the reason is unknown.

The compound of the present invention can also be incorporated in therinse bath or stabilizing bath to effectively eliminate thermostain. Theconcentration of the compound of the present invention in these baths ispreferably 10⁻³ to 0.5 times the concentration of the fixing agent inthe prebath.

The mesoionic compounds represented by the general formulae (III) and(IV) to be incorporated as fixing agents in the blix bath used in thesecond embodiment of the present invention will be describedhereinafter.

Preferred among mesoionic compounds to be used in the present inventionare those represented by the following general formula (III): ##STR10##wherein M represents a 5- or 6-membered heterocyclic group formed ofcarbon atom, nitrogen atom, oxygen atom, sulfur atom or selenium atom;and A₁.sup.⊖ represents --O.sup.⊖, --S.sup.⊖ or --N.sup.⊖ --R₁₁ in whichR₁₁ represents an alkyl group, a cycloalkyl group, an alkenyl group, analkynyl group, an aralkyl group, an aryl group or a heterocyclic group.

The general formula (III) will be further described hereinafter.

Examples of a 5-membered heterocyclic group represented by M includeimidazoliums, pyrazoliums, oxazoliums, thiazoliums, triazoliums,tetrazoliums, thiadiazoliums, oxadiazoliums, thiatriazoliums, andoxatriazoliums.

R₁₁ represents a substituted or unsubstituted alkyl group (e.g., methyl,ethyl, n-propyl, n-butyl, isopropyl, n-octyl, ethoxycarbonylmethyl,dimethylaminoethyl), a substituted or unsubstituted cycloalkyl group(e.g., cyclohexyl, 4-methylcyclohexyl, cyclopentyl), a substituted orunsubstituted alkenyl group (e.g., propenyl, 2-methylpropenyl), asubstituted or unsubstituted alkynyl group (e.g., propargyl, butynyl,1-methylpropargyl), a substituted or unsubstituted aralkyl group (e.g.,benzyl, 4-methoxybenzyl), a substituted or unsubstituted aryl group(e.g., phenyl, naphthyl, 4-methylphenyl, 3-methoxyphenyl,4-ethoxycarbonylphenyl), or a substituted or unsubstituted heterocyclicgroup (e.g., pyridyl, imidazolyl, morpholino, triazolyl, tetrazolyl,thienyl).

The heterocyclic group represented by M may be substituted by a nitrogroup, halogen atom (e.g., chlorine, bromine), mercapto group, cyanogroup, substituted or unsubstituted alkyl group (e.g., methyl, ethyl,propyl, t-butyl, methoxyethyl, methylthioethyl, dimethylaminoethyl,morpholinoethyl, methylthiomethyl, methoxyethoxyethoxyethyl,trimethylammonioethyl, cyanoethyl, phosphonomethyl, phosphonoethyl),aryl group (e.g., phenyl, 4-methanesulfonamidephenyl, 4-methylphenyl,3-methoxyphenyl, 4-dimethylaminophenyl, 3,4-dichlorophenyl, naphthyl),alkenyl group (e.g., allyl), cycloalkyl group (e.g., cyclohexyl,cyclopentyl), alkynyl group (e.g., propargyl), aralkyl group (e.g.,benzyl, 4-methylbenzyl, phenethyl, 4-methoxybenzyl), alkoxy group (e.g.,methoxy, ethoxy, methoxyethoxy, methylthioethoxy, dimethylaminoethoxy),aryloxy group (e.g., phenoxy, 4-methoxyphenoxy), alkylthio group (e.g.,methylthio, ethylthio, propylthio, methylthioethylthio,dimethylaminoethylthio, methoxyethylthio), arylthio group (e.g.,phenylthio, 4-dimethylaminophenylthio), heterocyclic oxy group (e.g.,2-pyridyloxy, 2-imidazolyloxy), heterocyclic thio group (e.g.,2-benzthiazolylthio, 4-pyrazolylthio), sulfonyl group (e.g.,methanesulfonyl, ethanesulfonyl, p-toluenesulfonyl,methoxyethylsulfonyl), carbamoyl group (e.g., substituted carbamoyl,methylcarbamoyl, dimethylaminoethylcarbamoyl, methoxyethylcarbamoyl,methylthioethylcarbamoyl, phenylcarbamoyl), thiocarbamoyl group (e.g.,dimethylthiocarbamoyl), sulfamoyl group (e.g., unsubstituted sulfamoyl,methylsulfamoyl, imidazolylethylsulfamoyl, phenylsulfamoyl), carbonamidegroup (e.g., acetamide, benzamide, methoxypropionamide,dimethylaminopropionamide), sulfonamide group (e.g., methanesulfonamide,benzenesulfonamide, p-toluenesulfonamide), acyloxy group (e.g.,acetyloxy, benzoyloxy), sulfonyloxy group (e.g., methanesulfonyloxy),ureide group (e.g. , unsubstituted ureide, methylureide, ethylureide,methoxyethylureide, dimethylaminopropylureide, methylthioethylureide,morpholinoethylureide, phenylureide), thioureide group (e.g.,unsubstituted thioureide, methylthioureide, methoxyethylthioureide),sulfamoylamino group (e.g., unsubstituted sulfamoyl,dimethylsulfamoylamino), acyl group (e.g., acetyl, benzoyl,4-methoxybenzoyl), thioacyl group (e.g., thioacetyl), heterocyclic group(e.g., 1-morpholino, 1piperidino, 2-pyridyl, 4-pyridyl, 2-thienyl,1pyrazolyl, 1-imidazolyl, 2-tetrahydrofuryl, tetrahydrothienyl),oxycarbonyl group (e.g., methoxycarbonyl, phenoxycarbonyl,methoxyethoxycarbonyl, methylthioethoxycarbonyl,methoxyethoxyethoxyethoxycarbonyl, dimethylaminoethoxycarbonyl,morpholinoethoxycarbonyl), oxycarbonylamino group (e.g.,methoxycarbonylamino, pohenoxycarbonylamino,2-ethylhexyloxycarbonylamino), amino group (e.g., unsubstituted amino,dimethylamino, methoxyethyiamino, anilino), carboxylic acid or saltthereof, sulfonic acid or salt thereof, or hydroxyl group.

The compound represented by the general formula (III) may form a salt(e.g., acetate, nitrate, salicylate, hydrochloride, iodate, bromate).

In the general formula (III), A₁.sup.⊖ preferably represents --S.sup.⊖.

Further preferred among mesoionic compounds which can be used in thepresent invention are those represented by the general formula (IV):##STR11## wherein X₁ represents N or C--R₁₃ ; Y₁ represents O, S, N orN--R₁₄ ; and Z represents N, N--R₁₅ or C--R₁₆.

R₁₂, R₁₃, R₁₄, R₁₅ and R₁₆ each represents an alkyl group, cycloalkylgroup, alkenyl group, alkynyl group, aralkyl group, aryl group,heterocyclic group, amino group, acylamino group, sulfonamide group,ureide group, sulfamoylamino group, acyl group, thioacyl group,carbamoyl group or thiocarbamoyl group.

R₁₃ and R₁₆ each may be a hydrogen atom. R₁₂ and R₁₃, R₁₂ and R₁₅, R₁₂and R₁₆, R₁₄ and R₁₅, and R₁₄ and R₁₆ may together form a ring.

The compound represented by the general formula (IV) will be furtherdescribed hereinafter.

R₁₂, R₁₃, R₁₄, R₁₅ and R₁₆ each represents a substituted orunsubstituted alkyl group (e.g., methyl, ethyl, n-propyl, t-butyl,methoxyethyl, methylthioethyl, dimethylaminoethyl, morpholinoethyl,dimethylaminoethylthioethyl, aminoethyl, methylthiomethyl,trimethylammonioethyl, phosphonomethyl, phosphonoethyl), substituted orunsubstituted cycloalkyl group (e.g., cyclohexyl, cyclopentyl,2-methylcyclohexyl), substituted or unsubstituted alkenyl group (e.g.,allyl, 2-methylallyl), substituted or unsubstituted alkynyl group (e.g.,propargyl), substituted or unsubstituted aralkyl group (e.g., benzyl,phenethyl, 4-methoxybenzyl), aryl group (e.g., phenyl, naphthyl,4-methylphenyl, 4-methoxyphenyl, 4-carboxyphenyl, 4-methylphenyl,3,4-disulfophenyl), substituted or unsubstituted heterocyclic group(e.g., 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-thienyl, 1-pyrazolyl,1-imidazolyl, 2-tetrahydrofuryl), substituted or unsubstituted aminogroup (e.g., unsubstituted amino, dimethylamino, methylamino), acylaminogroup (e.g., acetylamino, benzoylamino, methoxypropionylamino),sulfonamide group (e.g., methanesulfonamide, benzenesulfonamide,4-toluenesulfonamide), ureide group (e.g., unsubstituted ureide,3-methylureide), sulfamoylamino group (e.g., unsubstitutedsulfamoylamino, 3-methylsulfamoylamino), acyl group (e.g., acetyl,benzoyl), thioacyl group (e.g., thioacetyl), carbamoyl group (e.g.,unsubstituted carbamoyl, dimethylcarbamoyl), or thiocarbamoyl group(e.g., dimethylthiocarbamoyl). R₂ and R₅ each may be a hydrogen atom.

In the general formula (IV), X₁ preferably represents N or C--R₁₃. Y₁preferably represents N--R₁₄, S or O. Z preferably represents N orC--R₁₆. R₁₂, R₁₃ or R₁₆ each represents an unsubstituted or substitutedalkyl group, substituted or unsubstituted alkenyl group, substituted orunsubstituted alkynyl group or substituted or unsubstituted heterocyclicgroup. R₁₃ and R₁₆ each may be a hydrogen atom. R₁₄ is preferably asubstituted or unsubstituted alkyl group, substituted or unsubstitutedalkenyl group, substituted or unsubstituted alkynyl group, substitutedor unsubstituted heterocyclic group, substituted or unsubstituted aminogroup, substituted or unsubstituted thioacyl group, or substituted orunsubstituted thiocarbamoyl group.

Specific examples Of mesoionic compounds represented by the generalformulae (III) and (IV) to bemused in the second embodiment of thepresent invention will be set forth below, but the present inventionshould not be construed as being limited thereto. ##STR12##

The synthesis of the compound of the present invention represented bythe general formula (III) or (IV) can be accomplished by any suitablemethod as described in "Journal of Heterocyclic Chemistry" 2, 105(1965), "Journal of Organic Chemistry", 32, 2245 (1967), "Journal of theChemical Society" 3799 (1969), "Journal of the American ChemicalSociety" 80, 1895 (1958), "Chemical Communications", 1222 (1971),"Tetrahedron Letters" 2939 (1972), JP-A-60-87322, "Berichte derDeutschen Chemischen Gesellschaft", 38, 4049 (1905), "Journal of theChemical Society, Chemical Communications", 1224 (1971), JP-A-60-122936,JP-A-60-117240, "Advances in Heterocyclic Chemistry", 19, 1(1976),"Tetrahedron Letters", 5881 (1968), "Journal of Heterocyclic Chemistry"5, 277 (1968), "Journal of the Chemical Society, Perkin Transactions I",627 (1974), "Tetrahedron Letters", 1809 (1967) and 1578 (1971), "Journalof the Chemical Society", 899 (1935) and 2865 (1959), and "Journal ofOrganic Chemistry", 30, 567 (1965).

In the second embodiment of the present invention, it is described withreference to the use of a compound represented by the general formula(III) or (IV) that the system contains substantially no other fixingagents. This means that the system contains other fixing agents in anamount of 0.05 mol/l or less, preferably 0.01 mol/l or less. It was anunexpected fact that the compound of the present invention can beallowed to effectively serve as fixing agent by causing substantially noother fixing agents, e.g., commonly used thiosulfates to be contained inthe system. The amount of the compound of the present invention to beincorporated in the blix bath is such that it can serve as fixing agent,e.g., 1×10⁻¹ mol/l or more, preferably 1.5×10⁻¹ mol/l or more, morepreferably 2×10⁻¹ mol/l or more, particularly preferably 2×10⁻¹ to 3mol/l.

If the halogen composition of the silver halide emulsion contained inthe light-sensitive material to be processed is AgBrI (I≧1 mol %preferably 3 to 15 mol %), it is preferably used in an amount of 0.5 to2 mol/l, more preferably 1.2 to 2 mol/l. If the halogen composition isAgBr, AgBrCl or high silver chloride content (AgCl≧80 mol %), it ispreferably used in an amount of 0.2 to 0.9 mol/l, more preferably 0.4 to0.9 mol/l.

The former is normally for the case of light-sensitive material forpicture taking which has a relatively great coated amount of silver(e.g., 2 to 10 g/m²) while the latter is normally for the case oflight-sensitive material for print which has a relatively small coatedamount of silver (e.g., 0.4 to 0.9 g/m²).

In recent years, as the replenishment rate becomes lower, it has beendesired to further improve the solution stability of each processingsolution. The problem with the solution stability of the blix bath andits after-bath is precipitation of sulfides caused by oxidativedeterioration of thiosulfates used as fixing agents. The problem withthe rinse bath is caused by the introduction of the blix solution intothe rinse bath during processing. In order to inhibit the precipitation,sulfites are normally used as oxidation inhibitors. However, when alower replenishment rate is used, the precipitation problem can nolonger be solved by only increasing the amount of sulfites to be useddue to the limited solubility of sulfites or precipitation of Glauber'ssalt produced by the oxidation of sulfites.

The present inventors made extensive studies on fixing agents with anexcellent oxidative stability as substitute for thiosulfates. It wasfound that mesionic compounds have a fixing ability and are stable tooxidation and thus cause no precipitation even when a lowerreplenishment rate is used. Mesoionic compounds were also found toexhibit a smaller bleach fogging than thiosulfates and attain excellentresults particularly when used in combination with a high potentialoxidizer in a blix bath.

The reasons why mesoionic compounds exhibit an excellent oxidationresistance and good fixing properties can be believed as follows. Inparticular, --S.sup.⊖ group, --N.sup.⊖ R₁₁ group, etc. connected to thearomatic ring are relatively stable to oxidation. Since the charge of a--S.sup.⊖ group, --N.sup.⊖ R₁₁ group etc., has a structure that is notneutralized due to tautomerism, the mesoionic compounds containing a--S.sup.⊖ group, --N.sup.⊖ R₁₁ group etc. have a large affinity tosilver. However, the reasons for this are not clearly understood.

The reason why bleach fogging is improved when a mesoionic compound isused instead of a thiosulfate is believed to be that the amount of thedeveloping agent remaining in the film after processing is reduced. Theinventors are presently investigating this matter in greater detail.

The compound of the present invention can also be effectivelyincorporated in the rinse bath or stabilizing bath to inhibit theprecipitation in the rinse bath. The concentration of the compound ofthe present invention in the bath is preferably 10⁻³ to 0.5 times thatof the fixing agent in the prebath.

The silver halide color photographic material and the processing methodtherefor will be further described hereinafter.

The present silver halide color photographic light-sensitive materialcan comprise at least one blue-sensitive layer, at least onegreen-sensitive layer and at least one red-sensitive layer on a support.The number of silver halide emulsion layers and light-insensitive layersand the order of arrangement of these layers are not specificallylimited. In a typical embodiment, the present silver halide photographicmaterial comprises light-sensitive layers consisting of a plurality ofsilver halide emulsion layers having substantially the same colorsensitivity and different light sensitivities on a support. Thelight-sensitive layers are unit light-sensitive layers having a colorsensitivity to any of blue light, green light and red light. In themulti-layer silver halide color photographic material, these unitlight-sensitive layers are normally arranged in the order ofred-sensitive layer, green-sensitive layer and blue-sensitive layer asviewed from the support. However, the order of arrangement can beoptionally reversed depending on the purpose of application.Alternatively, two unit light-sensitive layers having the same colorsensitivity can be arranged with a unit light-sensitive layer having adifferent color sensitivity interposed therebetween.

Light-insensitive layers such as various interlayers can be providedbetween these silver halide light-sensitive layers and on the uppermostlayer and lowermost layer.

These interlayers can comprise couplers, DIR compounds or the like asdescribed in JP-A-61-43748, JP-A-59-113438, JP-A-59-113440,JP-A-61-20037 and JP-A-61-20038. These interlayers can further comprisea color stain inhibitor as commonly used.

The plurality of silver halide emulsion layers constituting each unitlight-sensitive layer can be preferably in a two-layer structure, i.e.,high sensitivity emulsion layer and low sensitivity emulsion layer, asdescribed in West German Patent 1,121,470 and British Patent 923,045. Ingeneral, these layers are preferably arranged in such an order that thelight sensitivity becomes lower towards the support. Furthermore, alight-insensitive layer can be provided between these silver halideemulsion layers. As described in JP-A-57-112751, JP-A-62-200350,JP-A-62-206541, and JP-A-62-206543, a low sensitivity emulsion layer canbe provided remote from the support while a high sensitivity emulsionlayer can be provided nearer to the support.

In an embodiment of such an arrangement, a low sensitivityblue-sensitive layer (BL), a high sensitivity blue-sensitive layer (BH),a high sensitivity green-sensitive layer (GH), a low sensitivitygreen-sensitive layer (GL), a high sensitivity red-sensitive layer (RH),and a low sensitivity red-sensitive layer (RL) can be arranged in thisorder remote from the support. In another embodiment, BH, BL, GL, GH,RH, and RL can be arranged in this order remote from the support. In afurther embodiment, BH, BL, GH, GL, RL, and RH can be arranged in thisorder remote from the support.

As described in JP-B-55-34932 (the term "JP-B" as used herein means an"examined Japanese patent publication"), a blue-sensitive layer, GH, RH,GL, and RL can be arranged in this order remote from the support.Alternatively, as described in JP-A-56-25738 and JP-A-62-63936, ablue-sensitive layer, GL, RL, GH, and RH can be arranged in this orderremote from the support.

As described in JP-B-49-15495, a layer arrangement can be used such thatthe uppermost layer is a silver halide emulsion layer having the highestlight sensitivity, the middle layer is a silver halide emulsion layerhaving a lower light sensitivity, and the lowermost layer is a silverhalide emulsion layer having a lower light sensitivity than that of themiddle layer. In such a layer arrangment, the light sensitivity becomeslower towards the support. Even if the layer structure comprises threelayers having different light sensitivities, a middle sensitivityemulsion layer, a high sensitivity emulsion layer and a low sensitivityemulsion layer can be arranged in this order remote from the support inthe same color-sensitive layer as described in JP-A-59-202464.

As described above, various layer structures and arrangements can beselected depending on the purpose of light-sensitive material.

If the silver halide color photographic material is a color negativefilm or color reverse film, a suitable silver halide to be incorporatedin the photographic emulsion layer is silver iodobromide, silveriodochloride or silver iodochlorobromide containing silver iodide in anamount of about 30 mol % or less. Particularly suitable is silveriodobromide or silver iodochlorobromide containing silver iodide in anamount of about 2 mol % to about 25 mol %.

If the silver halide color photographic material is a color photographicpaper, there can be used as silver halide to be contained in thephotographic emulsion layer silver chlorobromide or silver chloridesubstantially free of silver iodide. Specifically, the term"substantially free of silver iodide" means the silver iodide content of1 mol % or less, preferably 0.2 mol % or less. The halogen compositionof these silver chlorobromide emulsions may have arbitrary silverbromide/silver chloride ratio. This ratio can be widely selecteddepending on the purpose. Preferably, the proportion of silver chlorideis 2 mol % or more. Light-sensitive materials adapated for rapidprocessing preferably comprise a so-called high silver chloride emulsionhaving a high silver chloride content. The silver chloride content ofthese high silver chloride emulsions is preferably 90 mol % or more,more preferably 95 mol % or more. For the purpose of reducing thereplenishment rate of the developer, a substantially pure silverchloride emulsion having a silver chloride content of 98 to 99.9 mol %may be preferably used.

Silver halide grains in the photographic emulsion layers may beso-called regular grains having a regular crystal form, such as cube,octahedron and tetradecahedron, or those having an irregular crystalform such as sphere and tabular form, those having a crystal defect suchas twinning plane, or those having a combination of these crystal forms.

The silver halide grains may be either fine grains of about 0.2 μm orsmaller in diameter or giant grains having a projected area diameter orup to about 10 μm. The emulsion may be either a monodisperse emulsion ora polydisperse emulsion.

The preparation of the silver halide photographic emulsion which can beused in the present invention can be accomplished by any suitable methodas described in Research Disclosure, No. 17643 (December, 1978), pp.22-23, "I. Emulsion Preparation and Types", and No. 18716 (November,1979), page 648, Glafkides, "Chimie et Physique Photographique", PaulMontel (1967), G. F. Duffin, "Photographic Emulsion Chemistry", FocalPress, 1966, and V. L. Zelikman et al., "Making and Coating PhotographicEmulsion Focal Press", 1964.

Furthermore, monodisperse emulsions as described in U.S. Pat. Nos.3,574,628 and 3,655,394, and British Patent 1,413,748 can be preferablyused in the present invention.

Tabular grains having an aspect ratio of about 5 or more can be used inthe present invention. The preparation of such tabular grains can beeasily accomplished by any suitable method as described in Gutoff,"Photograpahic Science and Engineering", vol. 14, pp. 248-257, 1970,U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048, and 4,439,520, andBritish Patent 2,112,157.

The individual silver halide crystals may have either a homogeneousstructure or a heterogeneous structure composed of a core and an outershell differing in halogen composition, or may have a layered structure.Furthermore, the grains may have conjugated thereto a silver halidehaving a different halogen composition or a compound other than silverhalide, e.g., silver thiocyanate, lead oxide, etc. by an epitaxialjunction.

Mixtures of grains having various crystal forms may also be used.

The silver halide emulsion to be used in the present invention isnormally subjected to physical ripening, chemical ripening and spectralsensitization. During the physical ripening, various polyvalent metallicion impurities (e.g., salt or complex salt of cadmium, zinc, lead,copper, thallium, iron, ruthenium, rhodium, palladium, osmium, iridium,platinum) can be introduced into the system. As compounds for use in thechemical sensitization there can be used those described inJP-A-62-215272, lower right column on page 18--upper right column onpage 22. Additives to be used in these steps are described in ResearchDisclosure Nos. 17643 and 18716 as tabulated below. Known photographicadditives which can be used in the present invention are also describedin the above cited two references as shown in the table.

    ______________________________________                                        Kind of additive  RD17643    RD18716                                          ______________________________________                                        1.    Chemical sensitizer                                                                           p. 23      p. 648 right                                                       column (RC)                                             2.    Sensitivity increasing     do.                                                agent                                                                   3.    Spectral sensitizer                                                                           pp. 23-24  p. 648 RC-                                         and supersensitizer        p. 649 RC                                    4.    Brightening agent                                                                             p. 24                                                   5.    Antifoggant and pp. 24-25  p. 649 RC-                                         stabilizer                                                              6.    Light absorbent,                                                                              pp. 25-26  p. 649 RC-p.                                       filter dye, and            650 LC                                             ultraviolet                                                                   absorbent                                                               7.    Stain inhibitor p. 25 RC   p. 650 LC-RC                                 8.    Dye image stabilizer                                                                          p. 25                                                   9.    Hardening agent p. 26      p. 651 LC                                    10.   Binder          p. 26      do.                                          11.   Plasticizer and p. 27      p. 650 RC                                          lubricant                                                               12.   Coating aid and pp. 26-27  p. 650 RC                                          surface active agent                                                    13.   Antistatic agent                                                                              p. 27      do.                                          ______________________________________                                    

In order to inhibit deterioration in photographic properties due toformaldehyde gas, a compound capable of reacting with and solidifyingformaldehyde as disclosed in U.S. Pat. Nos. 4,411,987 and 4,435,503 canbe incorporated in the light-sensitive material.

The light-sensitive material to be processed in the present inventioncan comprise various color couplers. Specific examples of the colorcouplers are described in the patents described in the above citedResearch Disclosure No. 17643, VII-C to G.

Preferred yellow couplers include those described in U.S. Pat. Nos.3,933,501, 4,022,620, 4,326,024, 4,401,752, 4,248,961, 3,973,968,4,314,023, and 4,511,649, JP-B-58-10739, British Patents 1,425,020 and1,476,760, and European Patent 249,473A.

Preferred magenta couplers include 5-pyrazolone compounds andpyrazoloazole compounds. Particularly preferred are those described inU.S. Pat. Nos. 4,310,619, 4,351,897, 3,061,432, 3,725,064, 4,500,630,4,540,654, and 4,556,630, European Patent 73,636, JP-A-60-33552,JP-A-60-43659, JP-A-61-72238, JP-A-60-35730, JP-A-55-118034, andJP-A-60-185951, RD Nos. 24220 (June, 1984) and 24230 (June, 1984), andWO(PCT)88/04795.

Cyan couplers include naphthol and phenol couplers. Preferred are thosedescribed in U.S. Pat. Nos. 4,052,212, 4,146,396, 4,228,233, 4,296,200,2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308,4,334,011, 4,327,173, 3,446,622, 4,333,999, 4,753,871, 4,451,559,4,427,767, 4,690,889, 4,254,212, and 4,296,199, West German PatentApplication (OLS) No. 3,329,729, European Patents 121,365A and 249,453A,and JP-A-61-42658.

Colored couplers for correction of unnecessary absorptions of thedeveloped dye preferably include those described in Research DisclosureNo. 17643, VII-G, U.S. Pat. Nos. 4,163,670, 4,004,929, and 4,138,258,JP-B-57-39413, and British Patent 1,146,368. Furthermore, couplers forcorrection of unnecessary absorptions of the developed dye by afluorescent dye released upon coupling as described in U.S. Pat. No.4,774,181 and couplers containing as a releasable group a dye precursorgroup capable of reacting with a developing agent to form a dye asdescribed in U.S. Pat. No. 4,777,120 can be preferably used.

Couplers which form a dye having moderate diffusibility preferablyinclude those described in U.S. Pat. No. 4,366,237, British Patent2,125,570, European Patent 96,570, and West German Patent Appplication(OLS) No. 3,234,533.

Typical examples of polymerized dye-forming couplers are described inU.S. Pat. Nos. 3,451,820, 4,080,211, 4,367,282, 4,409,320, and4,576,910, and British Patent 2,102,173.

Couplers capable of releasing a photographically useful residual uponcoupling can also be used in the present invention. Preferred examplesof DIR couplers which release a developing inhibitor are described inthe patents cited in RD 17643, VII-F, JP-A-57-151944, JP-A-57-154234,JP-A-60-184248, and JP-A-63-37346, and U.S. Pat. Nos. 4,248,962, and4,782,012.

Couplers capable of imagewise releasing a nucleating agent or adeveloping accelerator at the time of development preferably includethose described in British Patents 2,097,140 and 2,131,188, andJP-A-59-157638 and JP-A-59-170840.

In addition to the foregoing couplers, the photographic materialaccording to the present invention can further comprise competingcouplers as described in U.S. Pat. No. 4,130,427, polyequivalentcouplers as described in U.S. Pat. Nos. 4,283,472, 4,338,393, and4,310,618, DIR redox compound-releasing couplers or DIRcoupler-releasing couplers or DIR coupler-releasing redox compounds orDIR redox-releasing redox compounds as described in JP-A-60-185950 andJP-A-62-24252, couplers capable of releasing a dye which returns to itsoriginal color after release as described in European Patent 173,302A,couplers capable of releasing a bleach accelerator as described in RDNos. 11449 and 24241, and JP-A-61-201247, couplers capable of releasinga ligand as described in U.S. Pat. No. 4,553,477, couplers capable ofreleasing a leuco dye as described in JP-A 63-75747, and couplerscapable of releasing a fluorescent dye as described in U.S. Pat. No.4,774,181.

The incorporation of these couplers in the light-sensitive material canbe accomplished by any suitable known dispersion method.

Examples of high boiling solvents to be used in the oil-in-waterdispersion process are described in U.S. Pat. No. 2,322,027. Specificexamples of high boiling organic solvents having a boiling point of 175°C. or higher at normal pressure which can be used in the oil-in-waterdispersion process include phthalic esters (e.g., dibutyl phthalate,dicylohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate,bis(2,4-di-t-amylphenyl)phthalate, bis(2,4-di-t-amylphenyl)isophthalate,bis(1,1-diethylpropyl)phthalate), phosphoric or phosphonic esters (e.g.,triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenylphosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate,tridodecyl phosphate, tributoxy ethyl phosphate, trichloropropylphosphate, di-2-ethylhexyl phenyl phosphonate), benzoic esters (e.g.,2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (e.g., N,N-diethyldodecanamide,N,N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols(e.g., isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylicesters (e.g., bis(2-ethylhexyl)sebacate, dioctyl azerate, glyceroltributylate, isostearyl lactate, trioctyl citrate), aniline derivatives(e.g., N,N-dibutyl-2-butoxy-5-tert-octylaniline), and hydrocarbons(e.g., paraffin, dodecylbenzene, diisopropyl naphthalene). As anauxiliary solvent there can be used an organic solvent having a boilingpoint of about 30° C. or higher, preferably 50° C. to about 160° C.Typical examples of such an organic solvent include ethyl acetate, butylacetate, ethyl propionate, methyl ethyl ketone, cyclohexanone,2-ethoxyethyl acetate, and dimethylformamide.

The process and effects of latex dispersion method and specific examplesof latexes to be used in dipping are described in U.S. Pat. No.4,199,363, West German Patent Application (OLS) No. 2,541,274, and2,541,230.

Alternatively, these couplers can be emulsion-dispersed in an aqueoussolution of hydrophilic colloid in the form of impregnation in aloadable latex polymer (e.g., U.S. Pat. No. 4,203,716) in the presenceor absence of the above mentioned high boiling organic solvent orsolution in a water-insoluble and organic solvent-soluble polymer.

Preferably, homopolymers or copolymers as described in InternationalPatent Disclosure WO88/00723, pp. 12-30, may be used. In particular,acrylamide polymers may be preferably used in view of dye stability.

The present invention is applicable to various types of colorlight-sensitive materials, particularly preferably to color negativefilms for common use or motion picture, color reversal films for slideor television, color papers, direct positive color light-sensitivematerials and color reversal papers.

Suitable supports which can be used in the present invention aredescribed in the above cited RD 17643 (page 28) and 18716 (right columnon page 647 to left column on page 648).

In the present light-sensitive material, the total thickness of allhydrophilic colloidal layers on the emulsion side is preferably in therange of 25 μm or less, more preferably 20 μm or less. The film swellingrate T_(1/2) is preferably in the range of 30 seconds or less, morepreferably 15 seconds or less. In- the present invention, the filmthickness is determined after being stored at a temperature of 25° C.and a relative humidity of 55% for 2 days. The film swelling rateT_(1/2) can be determined by a method known in the art, e.g., by meansof a swellometer of the type as described in A. Green et al.,"Photographic Science and Engineering" vol. 19, No. 2, pp. 124-129.T_(1/2) is defined as the time taken until half the saturated filmthickness is reached wherein the saturated film thickness is 90% of themaximum swollen film thickness reached when the light-sensitive materialis processed with a color developer at a temperature of 30° C. over 195seconds.

The film swelling rate T_(1/2) can be adjusted by adding a film hardenerto gelatin as binder or altering the ageing condition after coating. Thepercentage swelling of the light-sensitive material is preferably in therange of 150 to 400%. The percentage swelling can be calculated from themaximum swollen film thickness determined as described above inaccordance with the equation: (maximum swollen film thickness-filmthickness)/film thickness.

The above mentioned color photographic light-sensitive material can bedeveloped in accordance with an ordinary method as described in RD Nos17643 (pp. 28-29) and 18716 (left column--right column on page 651).

The color developer to be used in the development of the light-sensitivematerial is preferably an alkaline aqueous solution containing as a maincomponent an aromatic primary amine color developing agent. As such acolor developing agent there can be effectively used an aminophenoliccompound. In particular, p-phenylenediamine compounds are preferablyused. Typical examples of such p-phenylenediamine compounds include3-methyl-4-amino-N,N-diethylaniline,3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline,3-methyl-4-amino-N-ethyl-N-β-methanesulfonamideethylaniline,3-methyl-4-amino-N-ethyl-β-methoxyethylaniline, and sulfates,hydrochlorides and ptoluenesulfonates thereof. These compounds can beused in combination of two or more thereof depending on the purpose ofapplication.

The color developer normally contains a pH buffer such as carbonate,borate and phosphate of alkaline metal or a development inhibitor or foginhibitor such as bromides, iodides, benzimidazoles, benzothiazoles andmercapto compounds. If desired, the color developer may further containvarious preservatives such as hydroxylamine, diethylhydroxylamine,sulfites, hydrazines, phenylsemicarbazides, triethanolamine,catecholsulfonic acids andtriethylenediamine(1,4-diazabicyclo-[2,2,2]octane), organic solventssuch as ethylene glycol and diethylene glycol, development acceleratorssuch as benzyl alcohol, polyethylene glycol, quaternary ammonium salts,and amines, dye-forming couplers, competing couplers, fogging agentssuch as sodium boron hydride, auxiliary developing agents such as1-phenyl-3-pyrazolidone, viscosity-imparting agents, various chelatingagents exemplified by aminopolycarboxylic acids, aminopolyphosphonicacids, alkylphosphonic acids, and phosphonocarboxylic acids, (e.g.,ethylenediaminetetraacetic acid, nitrilotriacetic acid,diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid,hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonicacid, nitrilo-N,N,N-trimethylenephosphonic acid,ethylenediamine-N,N,N,N-tetramethylenephosphonic acid, andethylenediamine-di(o-hydroxyphenylacetic acid), and salts thereof),fluorescent brightening agent such as 4,4'-diamino-2,2-disulfostilbene,various surface active agents such as alkylsulfonic acid, arylsulfonicacid, aliphatic carboxylic acid and aromatic carboxylic acid, or thelike.

However, it is preferred that substantially no benzyl alcohol be used inthe system in view of pollution, ease of preparation of solution andinhibition of color stain. Specifically, the system may contain benzylalcohol in an amount of 2 ml or less per l of color developer, morepreferably none.

Reversal processing is usually carried out by black-and-whitedevelopment followed by color development. Black-and-white developers tobe used can contain one or more of known black-and-white developingagents, such as dihydroxybenzenes, e.g., hydroquinone, 3-pyrazolidones,e.g., 1-phenyl-3-pyrazolidone, and aminophenols, e.g.,N-methyl-p-aminophenol.

The color developer or black-and-white developer usually has a pH offrom 9 to 12. The replenishment rate of the developer is usually 3 l orless per m² of the light-sensitive material, though depending on thetype of the color photographic material to be processed. Thereplenishment rate may be reduced to 500 ml/m² or less by decreasing thebromide ion concentration in the replenisher. In particular, in the casewhere at so-called high silver chloride light-sensitive material used,excellent photographic properties and processability can be provided andthe fluctuation in photographic properties can be inhibited by reducingthe content of bromide ions and relatively increasing the content ofchloride ions in the color developer. In this case, the replenishmentrate can be reduced to about 20 ml per m² of light-sensitive materialwhere there is substantially no overflow in the color development bath.When the replenishment rate is reduced, it is preferred to prevent theevaporation of liquid and aerial oxidization by reducing the contactarea of processing bath with air. The replenishment rate can also bereduced by a means for suppressing accumuation of the bromide ion in thedeveloping solution.

The processing temperature with the present color developer is in therange of 20° to 50° C., preferably 30° to 45° C. The processing time isnormally in the range of 30 seconds to 3 minutes. The processing timecan be further reduced by carrying out color development at an elevatedtemperaure and a high pH value with a color developing solutioncontaining a color developing agent in a high concentration.

The photographic emulsion layer which has been color-developed isnormally subjected to bleach. However, in the first embodiment of thepresent invention, bleach may be effected simultaneously with fixation(i.e., blix), or these two steps may be carried out separately thesecond embodiment of the present invention, bleach and fixing aresimultaneously effected (blix). For speeding up of processing, bleachmay be followed by blix. Further, any of an embodiment wherein two blixbaths connected in series are used, an embodiment wherein blix ispreceded by fixation, and an embodiment wherein blix is followed bybleach may be selected arbitrarily according to the purpose. Bleachingagents to be used include compounds of polyvalent metals, e.g., iron(III), cobalt (III), chromium (IV) and copper (II), peroxides, quinones,and nitro compounds. Typical examples of these bleaching agents areferricyanides, bichromates, organic complex salts of iron (III) orcobalt (III) (e.g., aminopolycarboxylic acis, e.g.,ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid,cyclohexanediaminetetraacetic acid, methyliminodiacetic acid,1,3-diaminopropanetetraacetic acid, and glycol ether diaminetetraaceticacid, or complex salts of citric acid, tartaric acid, malic acid, etc),persulfates, bromates, permanganates, and nitrobenzenes. Of these,aminopolycarboxylic acid-iron (III) complex salts such as(ethylenediaminetetraacetato)iron (III) complex salts and persulfatesare preferred in view of speeding up of processing and conservation ofthe environment. In particular, aminopolycarboxylic acid-iron (III)complex salts are useful in both of a bleaching solution and a blixsolution.

The bleaching agent to be used in the present invention is preferably aso-called high potential oxidizer having a redox potential of 150 mV orhigher, preferably 180 mV or higher, more preferably 200 mV or higher.

In the present invention, the redox potential of the oxidizer can bedefined as value determined by the measurement method as described in"Transaction of the Faraday Society" vol. 55 (1959), pp. 1312-1313. Inthis case, the redox potential is determined at a pH value of 6.0 inaccordance with the above mentioned method. The reason why the potentialdetermined at a pH value of 6.0 is used is that the vicinity of thevalue of 6.0 gives a criterion for the generation of bleach fogging.

Specific examples of aminopolycarboxylic acid-iron (III) complex saltswill be set forth below with their redox potential as determined asdefined above, but the present invention should not be construed asbeing limited thereto. These aminopolycarboxylic acid-iron (III) complexsalts may be preferably used in the form of sodium, potassium orammonium salt, particularly in the form of ammonium salt in view ofbleaching speed.

    ______________________________________                                                             Redox potential                                          Compound No.         (mV vs. NHE; pH = 6)                                     ______________________________________                                        1.  N-(2-acetamide) iminodiacetic                                                                      180                                                      acid-iron (III) complex salt                                              2.  Methyliminodiacetic acid-iron                                                                      200                                                      (III) complex salt                                                        3.  Iminodiacetic acid-iron (III)                                                                      210                                                      complex salt                                                              4.  1,4-Butylenediaminetetraacetic                                                                     230                                                      acid-rion (III) complex salt                                              5.  Diethylenethioetherdiamine-                                                                        230                                                      tetraacetic acid-iron (III)                                                   complex salt                                                              6.  Glycoletherdiaminetetraacetic                                                                      240                                                      acid-iron (III) complex salt                                              7.  1,3-Propylenediaminetetraacetic                                                                    250                                                      acid-iron (III) complex salt                                              8.  Ethylenediaminetetraacetic                                                                         110                                                      acid-iron (III) complex salt                                              9.  Diethylenetriaminepentacetic                                                                        80                                                      acid-iron (III) complex salt                                              10. Trans-1,2-cyclohexanediamine-                                                                       80                                                      tetraacetic acid-iron (III)                                                   complex salt                                                              ______________________________________                                    

The pH value of the bleaching solution or blix solution comprising theseaminopolycarboxylic acid-iron (III) complex salts is normally in therange of 5.5 to 8. For speeding up a lower pH value can be processing,adopted.

The bleaching bath, blix bath or a prebath thereof can contain, ifdesired, a bleaching accelerator. Examples of useful bleachingaccelerators include compounds containing a mercapto group or adisulfide group as described in U.S. Pat. No. 3,893,858, West GermanPatents 1,290,812, and 2,059,988, JP-A-53-32736, JP-A-53-57831,JP-A-53-37418, JP-A-53-72623, JP-A-53-95630, JP-A-53-95631,JP-A-53-104232, JP-A-53-124424, JP-A-53-141623, and JP-A-53-28426, andResearch Disclosure No. 17129 (July, 1978), thiazolidine derivatives asdescribed in JP-A-50-140129, thiourea derivatives as described inJP-B-45-8506, JP-A-52-20832, JP-A-53-32735 and U.S. Patent 3,706,561,iodides as described in West German Patent 1,127,715 and JP-A-58-16235,polyoxyethylene compounds as described in West German Patents 966,410and 2,748,430, polyamine compounds as described in JP-B-45-8836,compounds as described in JP-A-49-42434, JP-A- 49-59644, JP-A-53-94927,JP-A-54-35727, JP-A-55-26506, and JP-A-58-163940, and bromine ions.Preferred among these compounds are compounds containing a mercaptogroup or disulfide group because of their great acceleratory effects. Inparticular, the compounds disclosed in U.S. Pat. No. 3,893,858, WestGerman Patent 1,290,812, and JP-A-53-95630 are preferred. The compoundsdisclosed in U.S. Pat. No. 4,552,834 are also preferred. These bleachingaccelerators may be incorporated into the light-sensitive material.These bleaching accelerators are particularly effective for blix ofcolor light-sensitive materials for picture taking.

The blix solution of the present invention may comprise known additivessuch as rehalogenating agent (e.g., ammonium bromide, ammoniumchloride), pH buffer (e.g., ammonium nitrate) and metal corrosioninhibitor (e.g., ammonium sulfate).

The fixing bath in the first embodiment of the present invention cancomprise known fixing agents besides the present compounds representedby the general formulae (I) and (II). Examples of such fixing agentsinclude thiosulfates, thiocyanates, thioethers, thioureas, and a largeamount of iodides. The thiosulfates are normally used, with ammoniumthiosulfate being applicable most preferably in view of solubility orfixing speed. These thiosulfates may be preferably used in combinationwith other fixing agents. As preservatives of the blix bath there can bepreferably used sulfites, bisulfites, carbonyl bisulfite adducts orsulfinic acid compounds. The fixing solution preferably containsaminopolycarboxylic acids or organic phosphonic chelating agents(preferably 1-hydroxyethylidene-1,1-diphosphonic acid andN,N,N',N'-ethylenediaminetetraphosphonic acid) for improving thestability.

The fixing solution can further contain various fluorescent brighteningagents, anti-foaming agents, surface active agents, polyvinylpyrrolidone, methanol or the like.

In the desilvering step, the agitation is preferably intensified as muchas possible to reduce the desilvering time. As agitating means there canbe used methods as described in JP-A-62-183460 and JP-A-62-183461. Inthe case where the processing solution may be jetted to the surface ofthe light-sensitive material, the collision of the processing solutionto the light-sensitive material is effected within 15 seconds from thetime at which the light-sensitive material is introduced into theprocessing solution.

In the present invention, the crossover time from the color developer tothe bleaching solution (time during which the light-sensitive materialis in the air between the time at which it comes out from the colordeveloper and the time at which it is introduced into the bleachingsolution) is preferably 10 seconds or less to eliminate bleach foggingor stain on the surface of the light-sensitive material. The crossovertime from the bleaching solution to the processing solution having afixing ability is preferably 10 seconds or less to prevent cyan dye frombeing disabled to restore its original color.

The replenishment rate of the fixing solution is preferably 800 ml/m² orless for color light-sensitive material for picture taking (e.g., havinga coated amount of silver of 4 to 12 g/m²). The replenishment rate ofthe blix solution is preferably 60 ml/m² or less.

As preservatives for the blix solution in the second embodiment of thepresent invention there can be used sulfites, bisulfites, carbonylbisulfite adducts or sulfinic acid compounds. The blix solutionpreferably contains aminopolycarboxylic acids or organic phosphonicchelating agents (preferably 1-hydroxyethylidene-1,1-diphosphonic acidand N,N,N',N'-ethylenediaminetetraphosphonic acid) for improving thestability.

The blix solution can further contain various fluorescent brighteningagents, anti-foaming agents, surface active agents, polyvinylpyrrolidone, methanol or the like.

In the desilvering step, the agitation is preferably intensified as muchas possible to reduce the desilvering time. As agitating means there canbe used methods as described in JP-A-62-183460 and JP-A-62-183461. Inthe case where the processing solution may be jetted to the surface ofthe light-sensitive material, the collision of the processing solutionto the light-sensitive material is effected within 15 seconds from thetime at which the light-sensitive material is introduced into theprocessing solution.

In the present invention, the crossover time from the color developer tothe blix solution (time during which the light-sensitive material is inthe air between the time at which it comes out from the color developerand the time at which it is introduced into the blix solution) ispreferably 10 seconds or less to eliminate bleach fogging or stain onthe surface of the light-sensitive material.

The replenishment rate of the blix solution is preferably 800 ml/m² orless for color light-sensitive material for picture taking (e.g., havinga coated amount of silver of 4 to 12 g/m²) or 60 ml/m² or less for colorphotographic paper.

It is usual that the thus desilvered silver halide color photographicmaterials of the present invention are subjected to washing and/orstabilization. The quantity of water to be used in the washing can beselected from a broad range depending on the characteristics of thelight-sensitive material (for example, the kind of couplers, etc.), theend use of the light-sensitive material, the temperature of washingwater, the number of washing tanks (number of stages), the replenishmentsystem (e.g., counter-flow system or direct-flow system), and othervarious factors. Of these factors, the relationship between the numberof washing tanks and the quantity of water in a multistage counter-flowsystem can be obtained according to the method described in "Journal ofthe Society of Motion Picture and Television Engineers", vol. 64, pp.248-253 (May, 1955).

According to the multi-stage counter-flow system described in the abovereference, although the requisite amount of water can be greatlyreduced, bacteria would grow due to an increase of the retention time ofwater in the tank, and floating masses of bacteria stick to thelight-sensitive material. In the present invention, in order to copewith this problem, the method of reducing calcium and magnesium ionconcentrations described in JP-A-62-288838 can be used very effectively.Further, it is also effective to use isothiazolone compounds orthiabenzazoles as described in JP-A-57-8542, chlorine typoebactericides, e.g., chlorinated sodium isocyanurate, benzotriazole, andbactericides described in Hiroshi Horiguchi, "Bokinbobaizai no kagaku"Eisei Gijutsu Kai (ed.), "Biseibutsu no mekkin, sakkin, bobaigijutsu",and Nippon Bokin Bobai Gakkai (ed.), "Bokin bobaizai jiten".

The washing water has a pH value of from 4 to 9, preferably from 5 to 8.The temperature of the water and the washing time can be selected frombroad ranges depending on the characteristics and end use of thelight-sensitive material, but usually ranges from 15° to 45° C. intemperature and from 20 seconds to 10 minutes in time, preferably from25° to 40° C. in temperature and from 30 seconds to 5 miniutes in time.The light-sensitive material of the present invention may be directlyprocessed with a stabilizer in place of the washing step. For the!stabilization, any of the known techniques as described in JP-A-57-8543,JP-A-58-14834, and JP-A-60-220345 can be used.

The aforesaid washing step may be followed by stabilization in somecases. For example, a stabilizing bath containing a dye stabilizer as isused as a final bath for color light-sensitive materials for picturetaking. Examples of such a dye stabilizer include formalin,hexamethylenetetramine, hexahydrotriazine, and N-methylol compounds.This stabilizing bath may also contain ammonium compounds, .compounds ofmetal such as Bi and Al, fluorescent brightening agents, variouschelating agents, film pH adjustors, film hardeners, germicides,anti-fungal agents, alkanolamine or surface active agents (preferablysilicone-based surface active agents) as necessary. As water to be usedin the rinse step or stabilizing step there may be preferably used tapwater, water which has been deionized with ion exchange resins such thatthe concentration of Ca ion and Mg ion are each reduced to 5 mg/l orless or water which has been sterilized with halogen, ultravioletbactericidal lamp or the like.

The replenishment rate of the above mentioned rinsing solution and/orstabilizing solution is preferably 1 to 50 times, preferably 2 to 30times, more preferably 2 to 15 times the amount of the processingsolution carried over from the prebath per unit area of thelight-sensitive material. The overflow accompanying replenishment of thewashing bath and/or stabilizing bath can be reused in other steps suchas desilvering.

The silver halide color light-sensitive material to be processed in thepresent invention may contain a color developing agent for the purposeof simplifying and expediting processing. Such a color developing agentis preferably used in the form of various precursors. Examples of suchprecursors include indoaniline compounds as described in U.S. Pat. No.3,342,597, Schiff's base type compounds as described in U.S. Pat. No.3,342,599, and Research Disclosure Nos. 14,850 and 15,159, and aldolcompounds as described in Research Disclosure No. 13,924, metalcomplexes as described in U.S. Pat. No. 3,719,492, and urethanecompounds as described in JP-A-53-135628.

The silver halide color light-sensitive material to be processed in thepresent invention may optionally comprise various1-phenyl-3-pyrazolidones for the purpose of accelerating colordevelopment. Typical examples of such compounds are described inJP-A-56-64339, JP-A-57-144547, and JP-A-58-115438.

In the present invention, the various processing solutions are used at atemperature of 10° C. to 50° C. The standard temperature range isnormally from 33° C. to 38° C. However, a higher temperature range canbemused to accelerate processing, reducing the processing time. On thecontrary, a lower temperature range can be used to improve the picturequality or the stability of the processing solutions. In order to savethe silver content in the light-sensitive material, processing methodscan be effected utilizing cobalt intensification or hydrogen peroxideintensification as described in West German Patent 2,226,770 and U.S.Pat. No. 3,674,499.

One of examples of silver halide color light-sensitive materials is onecomprising a direct positive type silver halide. The process for theprocessing of such a light-sensitive material will be describedhereinafter.

The silver halide color photographic material which has been imagewiseexposed to light is preferably color-developed with a surface developercontaining an aromatic primary amine color developer and having a pHvalue of 11.5 or less after or simultaneously with fogging by light ornucleating agent, and then subjected to bleach and fixing to form adirect positive color image thereon. The pH value of this developer ismore preferably in the range of 10.0 to 11.0.

The present fogging may be accomplished by either a so-called "lightfogging process" which comprises subjecting the entire surface of thelight-sensitive layer to second exposure or a so-called "chemicalfogging process" which comprises development in the presence of anucleating agent. The development may be effected in the presence of anucleating agent or fogging light. Alternatively, a light-sensitivematerial containing a nucleating agent may be subjected to fog exposure.

The light fogging process is described in Japanese Patent ApplicationNo. 61-253716, line 4 on page 47--line 5 on page 49. The nucleatingagent which can be used in the present invention is described in theabove cited Japanese Patent Application No. 61-253716, line 6 on page49--line 2 on page 67. In particular, compounds represented by thegeneral formulae [N-1] and [N-2] may be preferably used. Preferred amongthese compounds are those represented by the general formulae [N-I-1] to[N-I-10] set forth between page 56 and page 58 and the general formulae[N-II-1] to [N-II-12] set forth between page 63 and page 66 in the abovecited Japanese Patent Application No. 61-253716.

Nucleation acceletors which can be used in the present invention aredescribed in the above cited Japanese Patent Application No. 61-253716,line 11 on page 68--line 3 on page 71. Particularly preferred amongthese nucleation accelerators are those represented by the generalformula (A-1) to (A-13) set forth between page 69 and page 70 in theabove cited Japanese Patent Application No. 61-253716.

Color developers which can be used in the color development of thelight-sensitive material to be processed in the present invention aredescribed in the above cited Japanese Patent Application No. 61-253716,line 4 on page 71--line 9 on page 72. In particular, as aromatic primaryamine color developing agents there can be preferably usedp-phenylenediamine compounds. Typical examples of suchp-phenylenediamine compounds include3-methyl-4-amino-N-ethyl-N-(β-methanesulfonamideethyl) aniline,3-methyl-4-amino-N-ethyl-N-(β-hydroxyethyl) aniline,3-methyl-4-amino-N-ethyl-N-methoxyethylaniline, and sulfates andhydrochlorides thereof.

The first embodiment of the present invention can be applied to silverhalide black-and-white photographic materials. These silver halideblack-and-white photographic materials and processing methods thereofwill be further described hereinafter.

The halogen composition of the silver halide emulsion to be used in thepresent invention is not specifically limited and may be any of silverchloride, silver chlorobromide, silver iodobromide, silver bromide, andsilver iodobromochloride. The silver iodide content of the halogencomposition is preferably in the range of 10 mol % or less, particularly5 mol % or less.

The silver halide grains in the photographic emulsion layer to be usedin the present invention may have a relatively wide grain sizedistribution but preferably have a narrow grain size distribution. Inparticular, it is preferred that silver halide grains having a sizewithin ±40% from the average grain size account for 90% of all thegrains by weight or number.

Silver halide grains to be used for the formation of high contrastnegative images are preferably finely divided grains (e.g., having asize of 0.7 μm or less), particularly having a size of 0.5 μm or less.The size distribution of silver halide grains is not essentially limitedand is preferably monodisperse. The term "monodisperse" as used hereinmeans "being formed of grains wherein those having a size within ±40from the average grain size account for 95% of all the grains by weightor number".

The silver halide grains to be contained in the photographic emulsionmay have a regular crystal form such as cube, octahedron,rhombododecahedron and tetradecahedron, irregular form such as sphereand tabular form, or composite thereof.

The silver halide grains may be uniform such that the core and the shellthereof are the same in phase or heterogeneous such that they differ inphase.

In the silver halide emulsion to be used in the present invention, theremay be present cadmium salt, sulfite, lead salt, thallium salt, rhodiumsalt or complex salt thereof, iridium salt or complex salt thereof, etcduring the formation or physical ripening of silver halide grains.

The silver halide to be used in the present invention may be prepared inthe presence of an iridium salt or complex salt thereof in an amount of10⁻⁸ to 10⁻⁵ mol per mol of silver. The silver halide to be used in thepresent invention is also a silver haloiodide having a surface silveriodide content greater than the average silver iodide content. The useof an emulsion containing such a silver haloiodide can provide a highersensitivity and gamma value.

The silver halide emulsion to be used in the present process may or maynot be subjected to chemical sensitization. As processes for chemicalsensitization of the silver halide emulsion there have been known sulfursensitization process, reduction sensitization process and noble metalsensitization process. These chemical sensitization processes can beused singly or in combination.

As the noble metal sensitization process there can be typically usedgold sensitization process. In the gold sensitization process, there isused a gold compound, mainly gold complex salt. Noble metals other thangold, such as platinum, palladium and rhodium can be included. Specificexamples of such compounds are described in U.S. Pat. No. 2,448,060, andBritish Patent 618,016. As sulfur sensitizers there may be used sulfurcompounds contained in gelatin, various sulfur compounds such asthiosulfate, thiourea, thiazole and rhodanine, etc.

In the foregoing description, an iridium salt or rhodium salt may bepreferably used before the completion of physical ripening, particularlyduring the formation of grains, in the step of preparation of silverhalide emulsion.

In the present invention, the silver halide emulsion layer preferablycontains two kinds of monodisperse emulsions having different averagegrain sizes as disclosed in JP-A-61-223734 and JP-A-62-90646 withrespect to the rise in the maximum density (Dmax). The smaller sizemonodisperse grains are preferably subjected to chemical sensitization,most preferably sulfur sensitization. The larger size monodisperseemulsion may or may not be chemically sensitized. Since large sizemonodisperse grains are susceptible to black pepper, they are normallynot subjected to chemical sensitization. However, if subjected tochemical sensitization, they are preferably sparingly subjected tochemical sensitization to such an extent that no black peppers areproduced. Specifically, the sparing chemical sensitization can beaccomplished by employing a shorter chemical sensitization time or alower chemical sensitization temperature or a lower amount of chemicalsensitizer than that required for the chemical sensitization of smallsize grains. The difference in sensitivity between the large sizemonodisperse emulsion and the small size monodisperse emulsion is notspecifically limited and is normally in the range of 0.1 to 1.0,preferably 0.2 to 0.7 in terms of Δlog E, the sensitivity of the largesize monodisperse emulsion being preferably larger than the other. Theaverage grain size of the small size monodisperse grains is 90% or less,preferably 80% or less of that of the large size monodisperse silverhalide grains. The average grain size of the silver halide emulsiongrains is preferably in the range of 0.02μ to 1.0μ, more preferably 0.1μto 0.5μ. Preferably, the average grain size of the large sizemonodisperse grains and the small size monodisperse grains fall withinthis range.

If the light-sensitive material to be processed in the present inventioncomprises two or more kinds of emulsions having different sizes, thecoated amount of silver in the small size monodisperse emulsion ispreferably in the range of 40 to 90 wt %, more preferably 50 to 80 wt %based on the total coated amount of silver.

In the light-sensitive material to be processed in the presentinvention, monodisperse emulsions having different grain sizes may beincorporated in the same emulsion layer or separate emulsion layers. Ifmonodisperse emulsions are incorporated in separate layers, it ispreferred that a large size emulsion be incorporated in a layer abovethat for a small size emulsion.

The total coated amount of silver is preferably in the range of 1 g/m²to 8 g/m².

The light-sensitive material to be used in the present invention cancomprise sensitizing dyes as described in JP-A-55-52050, pp. 45-53(e.g., cyanine dye, melocyanine dye) for the purpose of improvingsensitivity. These sensitizing dyes may be used singly or incombination. Such a combination of sensitizing dyes may be usedparticularly for the purpose of supersensitization. In combination withsuch sensitizing dyes, a dye which doesn't exhibit a spectralsensitizing effect itself or a substance which doesn't substantiallyabsorb visible light but exhibits a supersensitizing effect may beincorporated in the emulsion. Useful sensitizing dyes, combinations ofsupersensitizing dyes, and supersensitizing substances are described inResearch Disclosure No. 17643, vol. 176 (December, 1978), page 23, IV-J.

The light-sensitive material to be processed in the present inventionmay comprise various compounds for the purpose of inhibiting foggingduring the preparation, storage or photographic processing oflight-sensitive material or stabilizing photographic properties. Forexample, many compounds known as fog inhibitor .and stabilizer can beused. Examples of such a fog inhibitor or stabilizer include azoles suchas benzothiazolium salt, nitroindazole, chlorobenzimidazole,bromobenzimidazole, mercaptothiazole, mercaptobenzothiazole,mercaptothiadiazole, aminotriazole, benzothiazole, andnitrobenzotriazole, mercaptopyrimidines, mercaptotriazines, thioketocompounds such as oxazolinthione, azaindenes such as triazaindene,tetraazaindene (particularly 4-hydroxy-substituted(1,3,3a,7)tetraazaindene), and pentaazaindene, benzenethiosulfonic acid,benzenesulfinic acid, and amide benzenesulfonate. Preferred among thesecompounds are benzotriazoles (e.g., 5-methyl-benzotriazole), andnitroindazoles (e.g., 5-nitroindazole). These compounds may beincorporated in the processing solutions.

The light-sensitive material to be processed in the present inventionmay comprise a nucleating agent in the photographic emulsion layer orother hydrophilic colloidal layers.

As nucleating agents to be incorporated in the present light-sensitivematerial there may be used those described in Research Disclosure Item23516 (November, 1983, page 346) and references cited therein, U.S. Pat.Nos. 4,080,207, 4,269,929, 4,276,346, 4,278,748, 4,385,108, 4,459,347,4,560,638, 4,478,928, and 4,686,167, British Patent 2,011,391B, EuropeanPatent 217,310, JP-A-60-179734, JP-A-62-270948, JP-A-63-29751,JP-A-61-170733, JP-A-61-27744, JP-A-62-948, JP-A-62-178246,JP-A-63-32538, JP-A-63-104047, JP-A-63-121838, JP-A-63-129337 ,JP-A-63-223744, JP-A-63-234244, JP-A-63-234245, JP-A-63-234246,JP-A-63-294552, JP-A-63-306438, JP-A-1-100530, JP-A-1-105941,JP-A-1-10594-3, JP-A-64-10233, and JP-A-1-90439, and Japanese PatentApplication Nos. 63-105682, 63-114118, 63-110051, 63-114119, 63-116239,63 -147339, 63-179760, 63-229163, 1-18377, 1- 18378, 1-18379, 1-15755,1-16814, 1-40792, 1-42615, 1-42616, 1-123693, and 1-126284.

As suitable development accelerators or nucleation infectiousdevelopment accelerators to be incorporated in the presentlight-sensitive material there can be effectively used compounds asdisclosed in JP-A-53-77616, JP-A-54-37732, JP-A-53-137133,JP-A-60-140340, and JP-A-60-14959 and various compounds containingnitrogen or sulfur atom.

The optimum amount of these accelerators depends on the kind thereof andis normally in the range of 1.0×10⁻³ to 0.5 g/m², preferably 5.0×10⁻³ to0.1 g/m².

The light-sensitive material to be processed in the present inventionmay comprise a desensitizer in the photographic emulsion layer or otherhydrophilic colloidal layers.

The organic desensitizer which can incorporated in the light-sensitivematerial to be used in the present invention can be specified bypolarographical half-wave potential, i.e., redox potential determined bypolarography. Specifically, the sum of polarographical anode potentialand cathod potential is positive. The process for the measurement ofpolarographical redox potential is described in, e.g., U.S. Pat. No.3,501,307. As such an organic desensitizer there can be preferably usedone containing at least one water-soluble group. Specific examples ofsuch a water-soluble group include sulfonic acid group, and carboxylicacid group. These groups may form salts with organic salt groups (e.g.,ammonia, pyridine, triethylamine, piperidine, morpholine) or alkalinemetals (e.g., sodium, potassium).

As such organic desensitizers there can be preferably used thoserepresented by the general formulae (III) to (V) as described inJP-A-63-133145.

The organic desensitizer to be incorporated in the light-sensitivematerial to be processed in the present invention is preferablyincorporated in the silver halide emulsion layer in an amount of1.0×10⁻⁸ to 10×10⁻⁴ mol/m² particularly 10×10⁻⁷ to 10×10⁻⁵ mol/m².

The light-sensitive material to be processed in the present inventionmay contain a water-soluble dye in the emulsion layer or otherhydrophilic colloidal layers as filter dye or for the purpose ofinhibiting irradiation or other various purposes. As such a filter dyethere can be a dye for further lowering photographic sensitivity,preferably an ultraviolet absorbent having a maximum spectral absorptionin the inherent sensitivity range of silver-halide or a dye having asubstantial light absorption mainly in the range of 38 nm to 600 nm forimproving the safety to safelight when treated as daylightlight-sensitive material.

These dyes may be preferably incorporated in the emulsion layer or in alayer above the silver halide emulsion layer, i.e., light-insensitivehydrophilic colloidal layer provided farther from the support than thesilver halide emulsion layer, together with a mordant.

The amount of such an ultraviolet absorbent to be incorporated dependson its molar absorptivity and is normally in the range of 10⁻² g/m² to 1g/m², preferably 50 mg/m² to 500 mg/m².

The above mentioned ultraviolet absorbent may be incorporated in acoating solution in the form of solution in a proper solvent such aswater, alcohol (e.g., methanol, ethanol, propanol), acetone, andmethylcellosolve or a mixture thereof.

As such ultraviolet absorbents there may be used benzotriazole compoundssubstituted by aryl group, 4-thiazolidone compounds, benzophenonecompounds, cinnamic ester compounds, butadiene compounds, benzoxazolecompounds or ultraviolet-absorbing polymers.

Specific examples of ultraviolet absorbents are described in U.S. Pat.Nos. 3,533,794, 3,314,794, 3,352,618, 3,705,805, 3,707,375, 4,045,229,3,700,455, and 3,499,863, JP-A-46-2784, and West German PatentPublication No. 1,547,863.

Examples of filter dyes include oxonol dyes, hemioxonol dyes, styryldyes, melocyanine dyes, cyanine dyes, and azo dyes. In order to reducecolors left after development, as filter dyes there may be preferablyused water-soluble dyes or dyes which are decolorized with an alkali orsulfurous acid ions.

Specific examples of such dyes include pyrazolone oxonol dyes asdescribed in U.S. Pat. No. 2,274,782, diarylazo dyes as described inU.S. Pat. No. 2,956,879, styryl dyes and butadienyl dyes as described inU.S. Pat. Nos. 3,423,207 and 3,384,487, melocyanine dyes as described inU.S. Pat. No. 2,527,583, melocyanine dyes and oxonol dyes as describedin U.S. Pat. Nos. 3,486,897, 3,652,284, and 3,718,472, enaminohemioxonoldyes as described in U.S. Pat. No. 3,976,661, and dyes as described inBritish Patents 584,609, and 1,177,429, JP-A-48-85130, JP-A-49-99620,and JP-A-49-114420, and U.S. Pat. Nos. 2,533,472, 3,148,187, 3,177,078,3,247,127, 3,540,887, 3,575,704, and 3,653,905.

These dyes may be incorporated in the coating solution for the presentlight-insensitive hydrophilic colloidal layer in the form of solution ina proper solvent such as water, alcohol (e.g., methanol, ethanol,propanol), acetone, and methylcellosolve or a mixture thereof.

The optimum amount of these dyes to be used is normally in the range of10⁻³ g/m² to 1 g/m², preferably 10⁻³ g/m² to 0.5 g/m².

The photographic light-sensitive material to be processed in the presentinvention may contain inorganic or organic film hardener in thephotographic emulsion layer or other hydrophilic colloidal layers. Forexample, chromium salts, aldehydes (e.g., formaldehyde, glutaraldehyde),N-methylol compounds (e.g., dimethylolurea), activated vinyl compounds(e.g., 1,3,5-triacryloyl-hexahydro-s-triazine,1,3-vinylsulfonyl-2propanol), activated halogen compounds (e.g.,2,4-dichloro-6-hydroxy-s-triazine), and mucohalogenic acids may be usedsingly or in combination.

The photographic emulsion layer or other hydrophilic colloidal layers inthe light-sensitive material to be processed in the present inventionmay comprise various surface active agents for the purpose offacilitating coating, inhibiting charging, emulsion dispersion andadhesion, and improving sliding properties and photographic properties(e.g., accelerating development, improving contrast, sensitization).Surface active agents which can be particularly preferably used in thepresent invention are polyalkylene oxides with a molecular weight of 600or more as described in JP-B-58-9412. If these surface active agents areused as antistatic agents, fluorine-containing surface active agents asdescribed in U.S. Pat. No. 4,201,586, and JP-A-60-80849, andJP-A-59-74554 can be particularly preferred.

The photographic emulsion to be incorporated in the presentlight-sensitive material may contain a matting agent such as silica,magnesium oxide and polymethyl methacrylate in the photographic emulsionlayer or other hydrophilic colloidal layers for the purpose ofinhibiting adhesion.

The photographic emulsion to be incorporated in the presentlight-sensitive material can contain a dispersion of a water-insolubleor sparingly water-soluble synthetic polymer for the purpose ofimproving dimensional stability or like purposes. For example, polymerscan be used comprising as monomeric units alkyl (meth)acrylate,alkoxyacryl (meth)acrylate, glycidyl (meth)acrylate, etc., singly or incombination, or combination thereof with acrylic acid, methacrylic acid,etc.

The present photographic light-sensitive material may preferably containa compound containing an acid group in the silver halide emulsion layerand other layers. Examples of such a compound containing an acid groupinclude organic acids such as salicylic acid, acetic acid and ascorbicacid, and polymers or copolymers containing as repeating units acidmonomers such as acrylic acid, maleic acid and phthalic acid. For thesecompounds, reference can be made to JP-A-61-223834, JP-A-61-228437,JP-A-62-25745, and JP-A-62-55642. Particularly preferred among thesecompounds are ascorbic acid as low molecular compound, and awater-dispersible latex of a copolymer comprising an acid monomer suchas acrylic acid and a crosslinkable monomer having two or moreunsaturated groups such as divinylbenzene as high molecular compound.

In the present invention, the developer to be used for the developmentof the silver halide black-and-white light-sensitive material maycontain commonly used additives (e.g., developing agent, alkaline agent,pH buffer, preservative, chelating agent). In the present processing,any known method can be used and any known processing solution can beused. The processing temperature is normally selected between 18° C. and50° C. but may fall below 18° C. or exceed 50° C.

The black-and-white developer may comprise known developing agents suchas dihydroxybenzenes, 1-phenyl-3 -pyrazolidones and aminophenols, singlyor in combination.

Examples of hydroxybenzene developing agents to be incorporated in theabove mentioned black-and-white developer include hydroquinone,chlorohydroquinone, bromohydroquinone, isopropylhydroquinone,methylhydroquinone, 2,3-dichlorohydroquinone, 2,3-dibromohydroquinone,and 2,5-dimethylhydroquinone. Particularly preferred among thesedeveloping agents is hydroquinone.

Examples of 1-phenyl-3-pyrazolidone or derivatives thereof as auxiliarydeveloping agents include 1-phenyl-3-pyrazolidone,1-phenyl-4,4-dimethyl-3-pyrazolidone,1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone,1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone,1-phenyl-5-methyl-3-pyrazolidone,1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, and1-p-tolyl-4,4-dimethyl-3-pyrazolidone.

Examples of p-aminphenolic auxiliary developing agents includeN-methyl-p-aminophenol, p-aminophenol, N-(β-hydroxyethyl-p-aminophenol,N-(4-hydroxyphenyl) glycine, 2-methyl-p-aminophenol, andp-benzylaminophenol. Particularly preferred among these compounds isN-methyl-p-aminophenol.

In general, the dihydroxybenzene developing agent is preferably used inan amount of 0.05 mol/l to 0.8 mol/l. If a combination ofdihydroxybenzenes and 1 -phenyl-3-pyrazolidones or p-aminophenols isused, it is preferred that the former be used in an amount of 0.05 mol/lto 0.5 mol/l while the latter be used in an amount of 0.06 mol/l orless.

Examples of sulfite preservatives to be used in the present inventioninclude sodium sulfite, potassium sulfite, lithium sulfite, sodiumbisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite.

The black-and-white developer particularly for graphic art may containsulfites in an amount of 0.3 mol/l or more. However, if sulfites areused in too large an amount, they are precipitated in the developer,contaminating the developer. Therefore, the upper limit of the amount ofsulfites to be used is preferably 1.2 mol/l.

Examples of alkaline agents to be incorporated in the present developerinclude pH adjustors or buffers such as sodium hydroxide, potassiumhydroxide, sodium carbonate, potassium carbonate, tribasic sodiumphosphate, tribasic potassium phosphate, sodium silicate and potassiumsilicate.

Examples of additives to be used besides the above mentioned componentsinclude compounds such as boric acid and borax, development inhibitorssuch as sodium bromide, potassium bromide and potassium iodide, organicsolvents such as ethylene glycol, diethylene glycol, triethylene glycol,dimethyl formamide, methyl cellosolve, hexylene glcyol, ethanol andmethanol, mercapto compounds such as 1-phenyl-5-mercaptotetrazole andsodium 2-mercaptobenzimidazole-5-sulfonate, indazole compounds such as5-nitroindazole, and fog inhibitors or black pepper inhibitors such asbenztriazole compound (e.g., 5-methylbenztriazole). Further, toners,surface active agents, anti-foaming agents, hard water softeners, filmhardeners, etc may be included as necessary.

The developer to be used in the present invention may comprise compoundsas described in JP-A-56-24347 as silver stain inhibitors, compounds asdescribed in JP-A-62-212651 as uneven development inhibitors, andcompounds as described in JP-A-61-267759 as dissolution aids.

The above mentioned developer may comprise as buffers boric acid asdescribed in JP-A-62-186259, saccharides (e.g., saccharose), oxims(e.g., acetoxim), phenols (e.g., 5-sulfosalicylic acid) and tribasicphosphates (e.g., sodium salt, potassium salt) or the like as describedin JP-A-60-93433.

The fixing solution to be used in the present invention is an aqueoussolution containing besides fixing agents a film hardener (e.g.,water-soluble aluminum compound), acetic acid and a dibasic acid (e.g.,tartaric acid, citric acid, salt thereof), preferably having a pH valueof 3.8 or more, more preferably 4.0 to 7.5.

The fixing bath to be used in the present invention may contain knownfixing agents in combination with the compound of the present invention.Examples of such fixing agents include sodium sulfate and ammoniumthiosulfate. In particular, ammonium thiosulfate may be preferably usedin view of fixing speed. The amount of the fixing agent to be used canbe properly altered and is normally in the range of about 0.1 mol/l toabout 5 mol/l. The water-soluble aluminum salt which serves mainly asfilm hardener in the fixing solution is a compound commonly known asfilm hardener for acidic film-hardening fixing solution. Examples ofsuch a compound include aluminum chloride, aluminum sulfate, andpotassium alum.

As the above mentioned dibasic acids there can be used tartatic acid orderivatives thereof and citric acid or derivatives thereof, singly or incombination. These compounds may be effectively incorporated in thefixing solution in an amount of 0.005 mol/l or more, particularly 0.01mol/l to 0.03 mol/l.

Specific examples of such dibasic acids include tartaric acid, potassiumtartarate, sodium tartarate, potassium sodium tartarate, ammoniumtartarate, and ammonium potassium tartarate.

Examples of citric acid and derivatives thereof which can be effectivelyused in the present invention include citric acid, sodium citrate, andpotassium citrate.

If necessary, the fixing solution may further contain a preservative(e.g., sulfite, bisulfite), a pH buffer (e.g., acetic acid, boric acid),a pH adjustor (e.g., ammonia, sulfuric acid), an image preservabilityimprover (e.g., potassium iodide), and a chelating agent. Such a pHbuffer is preferably used in an amount of 10 to 40 g/l, more preferably18 to 25 g/l because the pH value of the developer is high.

The fixing temperature and time are the same as that of development andare preferably in the range of about 20° C. to about 50° C. and 10seconds to 1 minute, respectively. The replenishment rate of the fixingsolution is preferably in the range of 400 ml/m² or less.

The rinse solution may contain an anti-fungal agent (e.g., compound asdescribed in Horiguchi, "Bokin Bobai no Kagaku", and JP-A-62-115154),rinse accelerator (e.g., sulfite), chelating agent or the like.

The replenishment rate of the rinse solution may be in the range of1,200 ml/l or less (including none). The case where the replenishmentrate of the rinse solution (or stabilizing solution) is zero means aso-called reservoir rinse process. As means for reducing thereplenishment rate there has been heretofore known a multi-stagecountercurrent process (e.g., two stages, three stages).

If any problem arises when the replenishment rate of water such as rinsewater is low, excellent processing properties can be obtained bycombining the following approaches.

The rinse bath or stabilizing bath may further contain isothiazolinecompounds as described in R. T. Kreiman, "J. Image, Tech.", vol. 10, No.6,242, 1984 and Research Disclosure Nos. 20,526, vol. 205, May 1981 and22,845, vol. 228, April 1983, compounds as described in JP-A-61-115154and JP-A-62-209532, or the like as microbiocides. In addition, the rinsebath or stabilizing bath may contain compounds as described in HiroshiHoriguchi, "Bokin Bobai no Kagaku", Sankyo Shuppan, 1982, Nihon BokinBobai Gakkai, "Bokin Bobai Gijutsu Handbook", Hakuhodo, 1986, L. E.West, "Water Quality Criteria", Photo. Sci. & Eng. Vol. 9, No. 6 (1965),M. W. Beach, "Microbiological Growths in Motion Picture Processing",SMPTE Journal Vol. 85 (1976), and R. O. Deegan, "Photo Processing WashWater Biocides", J. Imaging Tech. Vol. 10, No. 6 (1984).

If the light-sensitive material which has been processed in the presentmethod is washed with a small amount of water, it is further preferredthat there be provided a squeeze roller and a crossover rack washingtank as described in JP-A-63-18350 and JP-A-62-287252.

The overflow solution from the rinse bath or stabilizing bath caused byreplenishing the rinse bath or stabilizing bath to be used after thepresent processing with water treated with an anti-fungal agent can bepartially or entirely used as a processing solution having a fixingability as its prebath as described in JP-A-60-235133 andJP-A-63-129343. Further, a water-soluble surface active agent oranti-foaming agent may be incorporated in the system to inhibitunevenness due to bubbling upon rinse with a small amount of wash waterand/or transfer of components of the processing agent attached to thesqueeze rollers to the processed film.

In order to inhibit stain with a dye eluted from the light-sensitivematerial, a dye adsorbent as described in JP-A-63-163456 may beintroduced into the rinse bath.

In accordance with the above mentioned method, the photographic materialwhich has been developed and fixed is then rinsed and dried. The rinseis effected to entirely remove silver salts dissolved by fixing. Therinse is preferably effected at a temperature of about 20° C. to about50° C. for 10 seconds to 3 minutes. The drying is effected at atemperature of about 40° C. to about 100° C. The drying time can beproperly altered depending on the ambient conditions and is normally inthe range of about 5 seconds to 210 seconds.

Roller conveyor type automatic developing machines are described in U.S.Pat. Nos. 3,025,779 and 3,545,971 and will be simply referred to as"roller conveyor type processors" hereinafter. Roller conveyor typeprocessors consist of four step sections, i.e., development portion,fixing portion, rinse portion and drying portion. The process of thepresent invention doesn't exclude other steps (e.g., stop step). In themost preferred embodiment, the process of the present invention consistsof these four steps. In the rinse step, a 2- or 3-stage countercurrentrinse process can be employed to save water.

The developer to be used for the development of the light-sensitivematerial to be processed in the present invention is preferably storedin a wrapping material having a low oxygen permeability as described inJP-A-61-73147. The above mentioned developer may be preferably used witha replenishment system as described in JP-A-62-91939.

As previously mentioned, the first embodiment of the present inventioncan be applied to color photographic light-sensitive materials as wellas black-and-white light-sensitive materials. Examples of suchblack-and-white light-sensitive materials include ordinaryblack-and-white silver halide photographic materials (e.g.,black-and-white light-sensitive material for picture taking, X-rayblack-and-white light-sensitive material, black-and-whitelight-sensitive material for print), and infrared light-sensitivematerials for laser scanner.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention will be further described in the followingexamples, but the present invention should not be construed as beinglimited thereto.

Examples corresponding to the first embodiment of the present inventionwill be described as Examples 1 through 19.

EXAMPLE 1

A multilayer color light-sensitive material was prepared as Specimen 101by coating on a undercoated cellulose triacetate film support variouslayers having the following compositions.

Composition of Light-sensitive Layer

The coated amount of silver halide and colloidal silver is representedin g/m² as calculated in terms of amount of silver. The coated amount ofcoupler, additive and gelatin is represented in g/m². The coated amountof sensitizing dye is represented in mol per mol of silver halidecontained in the same layer.

    ______________________________________                                        1st Layer: anti-halation layer                                                Black colloidal silver   0.15                                                 Gelatin                  1.5                                                  ExM-8                    0.8                                                  UV-1                     0.03                                                 UV-2                     0.06                                                 Solv-2                   0.08                                                 UV-3                     0.07                                                 Cpd-5                    6 × 10.sup.-4                                  2nd Layer: interlayer                                                         Gelatin                  1.5                                                  UV-1                     0.03                                                 UV-2                     0.06                                                 UV-3                     0.07                                                 ExF-1                    0.004                                                Solv-2                   0.07                                                 Cpd-5                    6 × 10.sup.-4                                  3rd layer: 1st red-sensitive emulsion layer                                   Silver iodobromide emulsion                                                                            0.5                                                  (silver iodide content: 2 mol %,                                              internal high AgI type; grain                                                 diameter: 0.3 μm as calculated                                             in terms of sphere; coefficient of                                            fluctuation in grain diameter: 29%                                            as calculated in terms of sphere;                                             mixture of normal crystal and twin                                            crystal; diameter/thickness: 2.5)                                             Gelatin                  0.8                                                  ExS-1                    1.0 × 10.sup.-4                                ExS-2                    3.0 × 10.sup.-4                                ExS-3                    1 × 10.sup.-5                                  ExC-3                    0.22                                                 ExC-4                    0.02                                                 Cpd-5                    3 × 10.sup.-4                                  4th Layer: 2nd red-sensitive emulsion layer                                   Silver iodobromide emulsion                                                                            0.7                                                  (silver iodide content: 4 mol %;                                              internal high AgI type; grain                                                 diameter: 0.55 μm as calculated                                            in terms of sphere; coefficient of                                            fluctuation in grain diameter: 20%                                            as calculated in terms of sphere;                                             mixture of normal crystal and twin                                            crystal; diameter/thickness: 1)                                               Gelatin                  1.26                                                 ExS-1                    1 × 10.sup.-4                                  ExS-2                    3 × 10.sup.-4                                  ExS-3                    1 × 10.sup.-5                                  ExC-3                    0.33                                                 ExC-4                    0.01                                                 ExY-16                   0.01                                                 ExC-7                    0.04                                                 ExC-2                    0.08                                                 Solv-1                   0.03                                                 Cpd-5                    5 × 10.sup.-4                                  5th Layer: 3rd red-sensitive emulsion layer                                   Silver iodobromide emulsion                                                                            0.7                                                  (silver iodide content: 10 mol %;                                             internal high AgI type; grain                                                 diameter: 0.7 μm as calculated                                             in terms of sphere; coefficient of                                            fluctuation in grain diameter: 30%                                            as calculated in terms of sphere;                                             mixture of twin crystals; diameter/                                           thickness: 2)                                                                 Gelatin                  0.8                                                  ExS-1                    1 × 10.sup.-4                                  ExS-2                    3 × 10.sup.-4                                  ExS-3                    1 × 10.sup.-5                                  ExC-5                    0.05                                                 ExC-6                    0.06                                                 Solv-1                   0.15                                                 Solv-2                   0.08                                                 Cpd-5                    3 × 10.sup.-5                                  6th Layer: interlayer                                                         Gelatin                  1.0                                                  Cpd-5                    4 × 10.sup.-4                                  Cpd-1                    0.10                                                 Cpd-4                    1.23                                                 Solv-1                   0.05                                                 Cpd-3                    0.25                                                 7th Layer: 1st green-sensitive emulsion layer                                 Silver iodobromide emulsion                                                                            0.30                                                 (silver iodide content: 2 mol %;                                              internal high AgI type; grain                                                 diameter: 0.3 μ m as calculated                                            in terms of sphere; coefficient of                                            fluctuation in grain diameter: 28%                                            as calculated in terms of sphere;                                             mixture of normal crystal and twin                                            crystal; diameter/thickness: 2.5)                                             Gelatin                  0.4                                                  ExS-4                    5 × 10.sup.-4                                  ExS-6                    0.3 × 10.sup.-4                                ExS-5                    2 × 10.sup.-4                                  ExM-9                    0.2                                                  ExY-14                   0.03                                                 ExM-8                    0.03                                                 Solv-1                   0.2                                                  Cpd-5                    2 × 10.sup.-4                                  8th Layer: 2nd green-sensitive emulsion layer                                 Silver iodobromide emulsion                                                                            0.6                                                  (silver iodide content: 4 mol %;                                              internal high AgI type; grain                                                 diameter: 0.55 μm as calculated                                            in terms of sphere; coefficient of                                            fluctuation in grain diameter: 20%                                            as calculated in terms of sphere;                                             mixture of normal crystal and twin                                            crystal; diameter/thickness: 4)                                               Gelatin                  0.8                                                  ExS-4                    5 × 10.sup.-4                                  ExS-5                    2 × 10.sup.-4                                  ExS-6                    0.3 × 10.sup.-4                                ExM-9                    0.25                                                 ExM-8                    0.03                                                 ExM-10                   0.015                                                ExY-14                   0.04                                                 Solv-1                   0.2                                                  Cpd-5                    3 × 10.sup.-4                                  9th Layer: 3rd green-sensitive emulsion layer                                 Silver iodobromide emulsion                                                                            0.85                                                 (silver iodide content: 10 mol %;                                             internal high AgI type; grain                                                 diameter: 0.7 μ m as calculated                                            in terms of sphere; coefficient of                                            fluctuation in grain diameter: 30%                                            as calculated in terms of sphere;                                             mixture of normal crystal and twin                                            crystal; diameter/thickness: 2.0)                                             Gelatin                  1.0                                                  ExS-4                    2.0 × 10.sup.-4                                ExS-5                    2.0 × 10.sup.-4                                ExS-6                    0.2 × 10.sup.-4                                ExS-7                    3.0 × 10.sup.-4                                ExM-12                   0.06                                                 ExM-13                   0.02                                                 ExM-8                    0.02                                                 Solv-1                   0.20                                                 Solv-2                   0.05                                                 Cpd-5                    4 × 10.sup.-4                                  10th Layer: yellow filter layer layer                                         Gelatin                  0.9                                                  Yellow colloidal silver  0.05                                                 Cpd-1                    0.2                                                  Solv-1                   0.15                                                 Cpd-5                    4 × 10.sup.-4                                  11th Layer: 1st blue-sensitive emulsion layer                                 Silver iodobromide emulsion                                                                            0.4                                                  (silver iodide content: 4 mol %;                                              internal high AgI type; grain                                                 diameter: 0.5 μm as calculated                                             in terms of sphere; coefficient of                                            fluctuation in grain diameter: 15%                                            as calculated in terms of sphere;                                             octahedral grain)                                                             Gelatin                  1.0                                                  ExS-8                    2 × 10.sup.-4                                  ExY-16                   0.9                                                  ExY-14                   0.09                                                 Solv-1                   0.3                                                  Cpd-5                    4 × 10.sup.-4                                  12th Layer: 2nd blue-sensitive emulsion layer                                 Silver iodobromide emulsion                                                                            0.5                                                  (silver iodide content: 10 mol %;                                             internal high AgI type; grain                                                 diameter: 1.3 μm as calculated                                             in terms of sphere; coefficient of                                            fluctuation in grain diameter: 25%                                            as calculated in terms of sphere;                                             mixture of normal crystal and twin                                            crystal; diameter/thickness: 4.5)                                             Gelatin                  0.6                                                  ExS-8                    1 × 10.sup.-4                                  ExY-16                   0.12                                                 Solv-1                   0.04                                                 Cpd-5                    2 × 10.sup.-4                                  13th Layer: 1st protective layer                                              Finely divided silver iodobromide                                                                      0.2                                                  emulsion (average grain                                                       diameter: 0.07 μm; AgI content:                                            1 mol %)                                                                      Gelatin                  0.8                                                  UV-3                     0.1                                                  UV-4                     0.1                                                  UV-5                     0.2                                                  Solv-3                   0.04                                                 Cpd-5                    3 × 10.sup.-4                                  14th Layer: 2nd protective layer                                              Gelatin                  0.9                                                  Polymethyl methacrylate grains                                                                         0.2                                                  (diameter: 1.5 μm)                                                         Cpd-5                    4 × 10.sup.-4                                  H-1                      0.4                                                  ______________________________________                                    

In addition to the above mentioned components, a surface active agentwas incorporated in each of these layers as coating aid. Thus, Specimen101 was obtained.

The chemical structural formula and chemical name of the compounds usedherein will be set forth below. ##STR13##

The dried thickness of all the coat layers of Specimen 101 except thesupport and its subbing layer was 17.6 μm, and its swelling speed(T_(1/2)) was 8 seconds.

The specimen thus prepared was then cut into 35-mm wide strips. Thesestrips were then imagewise exposed to light, and subjected to runningprocessing in accordance with the following steps by means of anautomatic developing machine until the accummulated replenishment of thefixing solution reached 3 times the tank capacity.

    ______________________________________                                        Processing step                                                                                   Temper-   Replenish-                                                                            Tank                                    Step     Time       ature     ment rate*                                                                            capacity                                ______________________________________                                        Color    3 min. 15 sec.                                                                           38° C.                                                                           15 ml   20 l                                    development                                                                   Bleach   4 min. 30 sec.                                                                           38° C.                                                                           10 ml   40 l                                    Rinse    2 min. 10 sec.                                                                           35° C.                                                                           10 ml   20 l                                    Fixing   4 min. 20 sec.                                                                           38° C.                                                                           30 ml   30 l                                    Washing (1)                                                                            1 min. 05 sec.                                                                           35° C.                                                                           --      10 l                                    Washing (2)                                                                            1 min. 00 sec.                                                                           35° C.                                                                           20 ml   20 l                                    Stabilization                                                                          1 min. 05 sec.                                                                           38° C.                                                                           10 ml    0 l                                    Drying   4 min. 20 sec.                                                                           55° C.                                             ______________________________________                                         *Determined per 35mm width and 1m length                                 

The washing step was effected in a countercurrent process wherein thewashing water flows backward.

The various processing solutions had the following compositions:

    ______________________________________                                                        Running                                                                       Solution      Replenisher                                     ______________________________________                                        Color developer                                                               Diethylenetriamine-                                                                             1.0     g       1.1   g                                     pentaacetic acid                                                              1-Hydroxyethylidene-                                                                            3.0     g       3.2   g                                     1,1-diphosphonic acid                                                         Sodium sulfite    4.0     g       4.9   g                                     Potassium carbonate                                                                             30.0    g       30.0  g                                     Potassium bromide 1.4     g       --                                          Potassium iodide  1.5     mg      --                                          Hydroxylamine sulfate                                                                           2.4     g       3.6   g                                     4-[N-ethyl-N-(β-                                                                           4.5     g       7.2   g                                     hydroxyethyl)amino]                                                           aniline sulfate                                                               Water to make     1.0     l       1.0   l                                     pH                10.05           10.10                                       Bleaching solution                                                            Ferric ammonium 1,3-                                                                            144.0   g       206.0 g                                     propylenediamine-                                                             tetraacetate monohydrate                                                      Ammonium bromide  84.0    g       12.0  g                                     Ammonium sulfate  30.0    g       41.7  g                                     98% Acetic acid   28.0    g       40.0  g                                     Hydroxyacetic acid                                                                              63.0    g       90.0  g                                     Water to make     1.0     l       1.0   l                                     27% Aqueous ammonia                                                                             pH 3.0          pH 2.8                                      to make                                                                       Fixing solution                                                               Disodium ethylenediamine-                                                                       0.5     g       1.0   g                                     tetraacetate                                                                  Sodium sulfite    7.0     g       12.0  g                                     Sodium bisulfite  5.0     g       9.5   g                                     Fixing agent      170.0   ml      240.0 ml                                    70 wt. % Aqueous solution                                                     of ammonium thiosulfate                                                       or fixing agent as set                                                                          0.8     mol     1.1   mol                                   forth in Table 1                                                              Water to make     1.0     l       1.0   l                                     pH                6.7             6.7                                         ______________________________________                                    

Washing Solution (The running solution was used also as replenisher)

Tap water was passed through a mixed bed column packed with an H-typestrongly acidic cation exchange resin (Amberlite IR-120B available fromRohm & Haas) and an OH-type anion exchange resin (Amberlite IR-400available from the same company) so that the calcium and magnesium ionconcentrations were each reduced to 3 mg/l or less. Dichlorinated sodiumisocyanurate and sodium sulfate were then added to the solution inamounts of 20 mg/l and 0.15 g/l, respectively.

The washing solution thus obtained had a pH value of 6.5 to 7.5.

    ______________________________________                                        Stabilizing solution                                                                            Running                                                                       Solution    Replenisher                                     ______________________________________                                        37% Formalin        2.0    ml     3.0  ml                                     Polyoxyethylene-p-  0.3    g      0.45 g                                      monononylphenylether                                                          (mean polymerization degree:                                                  10)                                                                           Disodium ethylenediamine-                                                                         0.05   g      0.08 g                                      tetraacetate                                                                  Water to make       1.0    l      1.0  l                                      pH                  5.0-8.0       5.0-8.0                                     ______________________________________                                    

The specimen which had been subjected to running processing was thensubjected to fixing for 2 minutes and 3 minutes.

The specimens thus processed were then measured for amount of silverleft on the unexposed portion by X-ray fluorescence.

Another batch of the specimen which had been subjected to runningprocessing was stored at a temperature of 60° C. and a relative humidityof 70% for 10 days. The change in the minimum density of magenta (ΔDmin)between before and after storage was determined.

Comparative specimens were prepared in the same manner as in Specimen101 except that the compound of the present invention was replaced bythe following comparative compound (A) as described in U.S. Pat. No.4,378,424, the comparative compounds (B) and (C) as described inJP-A-1201659, and the comparative compound (D) as described inJP-A-2-44355 in the equimolecular amount, respectively. Thesecomparative specimens were then subjected to the same tests as describedabove. ##STR14##

The results are set forth in Table 1.

Table 1 shows that the use of the compound of the present invention asfixing agent can provide excellent results, i.e., excellent desilveringproperties upon rapid processing and little stain after heat andhumidity test.

                  TABLE 1                                                         ______________________________________                                               Residual  Change in minimum                                                   amount of magenta density                                                     silver (μg/cm.sup.2)                                                                 (ΔDmin) between                                        Fixing   2-min.  3-min.  before and after                                     agent    fixing  fixing  thermal test                                                                              Remarks                                  ______________________________________                                        Ammonium 25.0    4.0     +0.07       Compara-                                 thiosulfate                          tive                                     Compound 5.1     0.7     +0.03       Present                                  A-1                                  Invention                                Compound 5.8     0.7     +0.03       Present                                  A-2                                  Invention                                Compound 5.7     0.7     +0.03       Present                                  A-6                                  Invention                                Comparative                                                                            10.0    0.8     +0.10       Compara-                                 Compound A                           tive                                     Comparative                                                                            9.0     0.8     +0.8        Compara-                                 Compound B                           tive                                     Comparative                                                                            9.1     0.7     +0.08       Compara-                                 Compound C                           tive                                     Comparative                                                                            0.5     0.8     +0.09       Compara-                                 Compound D                           tive                                     ______________________________________                                    

EXAMPLE 2

Specimens were prepared in the same manner as in Specimen 101 exceptthat Compound A-1 was replaced by. Compounds A-3, A-5, A-7, A-9 andA-13, respectively, and then subjected to the same tests as in Example1.

As a result, it was found that the use of the fixing agents of thepresent invention can provide excellent properties as in Example 1,i.e., excellent image preservability (after heat and humidity test) andexcellent desilvering properties (fixining properties) upon rapidprocessing.

EXAMPLE 3

A color negative film for picture taking which had been prepared in thesame manner as in Example 2 in JP-A-2-93641 was imagewise exposed tolight by means of a sensitometer (Type FWH, available from Fuji PhotoFilm Co., Ltd.).

The specimen was then subjected to continuous processing (running test)in the following steps by means of an automatic developing machine forcolor negative film until the replenishment reached twice the capacityof the fixing bath.

    ______________________________________                                        Processing step                                                                                    Temper-  Replenish-                                                                            Tank                                    Step     Time        ature    ment rate*                                                                            capacity                                ______________________________________                                        Color    3 min.  15 sec. 38° C.                                                                        23 ml   15 l                                  development                                                                   Bleach           50 sec. 38° C.                                                                         5 ml   5 l                                   Blix             50 sec. 38° C.                                                                        --      5 l                                   Fixing           50 sec. 38° C.                                                                        16 ml   5 l                                   Washing (1)      30 sec. 38° C.                                                                        --      3 l                                   Washing (2)      20 sec. 38° C.                                                                        34 ml   3 l                                   Stabilization    20 sec. 38° C.                                                                        20 ml   3 l                                   Drying   1 min.          55° C.                                        ______________________________________                                         *Determined per 35mm width and 1m length                                 

The washing step was effected in a countercurrent process wherein thewashing water flows backward. The overflow from the washing tanks wereall introduced into the fixing bath. In the automatic developingmachine, the upper portion of the bleaching bath and the lower portionof the blix bath, and the upper portion of the fixing bath and the lowerportion of the blix bath were connected to each other via a pipe so thatthe overflow produced by the supply of the replenisher to the bleachingbath and the fixing bath entirely flew into the blix bath. The amount ofthe developer brought over to the bleaching step, the amount of thebleaching solution brought over to the blix step, and the amount of thefixing solution brought over to the washing step were 2.5 ml, 2.0 ml,and 2.0 ml per m of 35-mm wide light-sensitive material, respectively.The time for crossover was 5 seconds in all the steps. This crossovertime is included in the processing time at the previous step.

The various processing solutions had the following compositions:

    ______________________________________                                                         Running                                                                       Solution     Replenisher                                     ______________________________________                                        Developer                                                                     Diethylenetriamine-                                                                              2.0    g       2.2  g                                      pentaacetic acid                                                              1-Hydroxyethylidene-                                                                             3.3    g       3.3  g                                      1,1-diphosphonic acid                                                         Sodium sulfite     3.9    g       5.2  g                                      Potassium carbonate                                                                              37.5   g       39.0 g                                      Potassium bromide  1.4    g       0.4  g                                      Potassium iodide   1.3    mg      --                                          Hydroxylamine sulfate                                                                            2.4    g       3.3  g                                      2-Methyl-4-[N-ethyl-N-                                                                           4.5    g       6.1  g                                      (β-hydroxyethyl)amino]                                                   aniline sulfate                                                               Water to make      1.0    l       1.0  l                                      pH                 10.05          10.15                                       Bleaching solution                                                            Ferric ammonium 1,3-                                                                             144.0  g       206.0                                                                              g                                      propylenediamine-                                                             tetraacetate monohydrate                                                      Ammonium bromide   84.0   g       120.0                                                                              g                                      Ammonium nitrate   17.5   g       25.0 g                                      Hydroxyacetic acid 63.0   g       90.0 g                                      Acetic acid        33.2   g       47.4 g                                      Water to make      1.0    l       1.0  l                                      pH adjusted with aqueous                                                                         3.20           2.80                                        ammonia                                                                       ______________________________________                                    

Blix Solution (running solution)

15:85 Mixture of the running solution of the bleaching bath and therunning solution of the fixing bath.

    ______________________________________                                        Fixing solution                                                                               Running                                                                       Solution      Replenisher                                     ______________________________________                                        Ammonium sulfite  19.0   g        57.0 g                                      Aqueous solution of                                                                             280    ml       840  ml                                     ammonium thiosulfate                                                          (700 g/l)                                                                     or fixing agent of the                                                                          1.32   mol      3.97 mol                                    present invention                                                             Imidazole         28.5   g        85.5 g                                      Ethylenediaminetetraacetic                                                                      12.5   g        37.5 g                                      acid                                                                          Water to make     1.0    l        1.0  l                                      pH adjusted with aqueous                                                                        7.40            7.45                                        ammonia and acetic acid                                                       ______________________________________                                    

Washing Solution (The running solution was used also as replenisher)

Tap water was passed through a mixed bed column packed with an H-typestrongly acidic cation exchange resin (Amberlite IR-120B available fromRohm & Haas) and an OH-type strongly basic anion exchange resin(Amberlite IRA-400 available from the same company) so that the calciumand magnesium ion concentrations were each reduced to 3 mg/l or less.Dichlorinated sodium isocyanurate and sodium sulfate were then added tothe solution in amounts of 20 mg/l and 150 mg/l, respectively. Thewashing solution thus obtained had a pH value of 6.5 to 7.5.

    ______________________________________                                        Stabilizing solution (The running                                             solution was also used as replenisher)                                        ______________________________________                                        37% Formalin              2.0    ml                                           Polyoxyethylene-p-monononylphenylether                                                                  0.3    g                                            (mean polymerization degree: 10)                                              Disodium ethylenediaminetetraacetate                                                                    0.05   g                                            Water to make             1.0    l                                            pH                        5.0-8.0                                             ______________________________________                                    

The specimen which had been subjected to running processing was thensubjected to fixing for 40 seconds and 45 seconds.

The specimens thus processed were then measured for amount of silverleft on the unexposed portion by X-ray fluorescence.

Another batch of the specimen which had been subjected to runningprocessing was stored at a temperature of 60° C. and a relative humidityof 70% for 10 days. The change in the minimum density of magenta (ΔDmin)between before and after storage was determined.

Comparative specimens were prepared in the same manner as in Specimen101 except that the compound of the present invention was replaced byComparative Compounds (A), (B), (C) and (D) in the equimolecular amount,respectively. These comparative specimens were then subjected to thesame tests as described above.

The results are set forth in Table 2.

Table 2 shows that the use of the compound of the present invention asfixing agent can provide excellent results, i.e., excellent desilveringproperties upon rapid processing and little stain after heat andhumidity test.

                  TABLE 2                                                         ______________________________________                                               Residual  Change in minimum                                                   amount of magenta density                                                     silver (μg/cm.sup.2)                                                                 (ΔDmin) between                                        Fixing   40-sec. 45-sec. before and after                                     agent    fixing  fixing  thermal test                                                                              Remarks                                  ______________________________________                                        Ammonium 20      1.1     +0.06       Compara-                                 thiosulfate                          tive                                     Compound 1.1     0.8     +0.03       Present                                  A-1                                  Invention                                Compound 1.3     0.9     +0.03       Present                                  A-2                                  Invention                                Compound 1.2     0.8     +0.03       Present                                  A-6                                  Invention                                Comparative                                                                            7.5     0.9     +0.10       Compara-                                 Compound A                           tive                                     Comparative                                                                            7.3     0.9     +0.8        Compara-                                 Compound B                           tive                                     Comparative                                                                            6.8     0.9     +0.07       Compara-                                 Compound C                           tive                                     Comparative                                                                            7.2     0.9     +0.08       Compara-                                 Compound D                           tive                                     ______________________________________                                    

EXAMPLE 2

Specimens were prepared in the same manner as in Example 3 except thatCompound A-1 was replaced by Compounds A-3, A-4, A-5, A-7, A-8, A-9,A-12, A-13, A-14, A-17, A-18, A-20, A-22, A-24, A-29, A-30, A-31, A-39,A-43, A-45, A-52, and A-54, respectively, and then subjected to the sametests as in Example 3.

As a result, it was found that the use of the fixing agents of thepresent invention can provide excellent properties as in Example 3,i.e., little thermostain after heat and humidity test and excellentdesilvering properties (fixing properties) upon rapid processing.

EXAMPLE 5

A multi-layer color photographic paper was prepared by coating on apolyethylene double-laminated paper support various layers having thefollowing compositions. The coating solutions for the various layerswere prepared as follows:

Preparation of 1st Layer Coating Solution

19.1 g of a yellow coupler (ExY), 4.4 g of a dye image stabilizer(Cpd-1) and 0.8 g of a dye image stabilizer (Cpd-7) were dissolved in27.2 cc of ethyl acetate and 8.2 g of a solvent (Solv-1). The solutionwas then emulsion-dispersed in 185 cc of a 10% aqueous solution ofgelatin containing 8 cc of 10% sodium dodecylbenzenesulfonate. On theother hand, to a silver chlorobromide emulsion (3:7 (silver molar ratio)of an emulsion of cubic grains with an average grain size of 0.88 μm anda grain size distribution fluctuation coefficient of 0.08 and anemulsion of cubic grains with an average grain size Of 0.70 μm and agrain size distribution fluctuation coefficient of 0.10, each emulsioncomprising 0.2 mol % silver bromide localized thereon) was added ablue-sensitive sensitizing dye as set forth below in an amount of2.0×10⁻⁴ mol per mol of silver for large size emulsion and 2.5×10⁻⁴ molper mol of silver for small size emulsion. The emulsion was thensubjected to sulfur sensitization. The emulsion dispersion previouslyprepared and the emulsion thus prepared were mixed to prepare the firstlayer coating solution having the composition as set forth below.

Coating solutions for the 2nd to 7th layers were prepared in the samemanner as in the 1st layer coating solution. As gelatin hardener foreach of these layers there was used sodium salt of1-oxy-3,5-dichloro-s-triazine.

As spectral sensitizing dyes for each of these layers there were usedthe following compounds: ##STR15##

To the red-sensitive emulsion layer was added the following compound inan amount of 2.6×10⁻³ mol per mol of silver halide: ##STR16##

To the blue-sensitive emulsion layer, the green-sensitive emulsion layerand the red-sensitive emulsion layer was added1-(5-methylureidephenyl)-5-mercaptotetrazole in amounts of 8.5×10⁻⁵ mol,7.7×10⁻⁴ mol and 2.5×10⁻⁴ mol per mol of silver halide, respectively.

To the blue-sensitive emulsion layer and the green-sensitive emulsionlayer was added 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene in amounts of1×10⁻⁴ mol and 2×10⁻⁴ mol per mol of silver halide, respectively.

In order to inhibit irradiation, the following dyes were added to theemulsion layer. ##STR17##

Layer Structure

The composition of the various layers will be set forth below. Thefigure indicates the coated amount of each component (g/m²). The coatedamount of silver halide emulsion is represented as calculated in termsof silver.

Support

Polyethylene-laminated paper [Polyethylene on the 1st layer sidecontains a white pigment (TiO₂) and a bluish dye (ultramarine)]

    __________________________________________________________________________    1st layer: blue-sensitive layer                                               Previously mentioned silver                  0.30                             chlorobromide emulsion                                                        Gelatin                                      1.86                             Yellow coupler (ExY)                         0.82                             Dye image stabilizer (Cpd-1)                 0.19                             Solvent (Solv-1)                             0.35                             Dye image stabilizer (Cpd-7)                 0.06                             2nd layer: color stain inhibiting layer                                       Gelatin                                      0.99                             Color stain inhibitor (Cpd-5)                0.08                             Solvent (Solv-1)                             0.16                             Solvent (Solv-4)                             0.08                             3rd layer: green-sensitive layer                                              Silver chlorobromide emulsion (1:3           0.12                             (Ag molar ratio) mixture of cubic                                             grains with an average grain size                                             of 0.55 μm and a grain size distribution                                   fluctuation coefficient of 0.10 and                                           cubic grains with an average grain                                            size of 0.39 μm and a grain size                                           distribution fluctuation coefficient                                          of 0.08, each emulsion comprising                                             0.8 mol % AgBr localized thereon)                                             Gelatin                                      1.24                             Magenta coupler (ExM)                        0.20                             Dye image stabilizer (Cpd-2)                 0.03                             Dye image stabilizer (Cpd-3)                 0.15                             Dye image stabilizer (Cpd-4)                 0.02                             Dye image stabilizer (Cpd-9)                 0.02                             Solvent (Solv-2)                             0.40                             4th layer: ultraviolet absorbing layer                                        Gelatin                                      1.58                             Ultraviolet absorbent (UV-1)                 0.47                             Color stain inhibitor (Cpd-5)                0.05                             Solvent (Solv-5)                             0.24                             5th layer: red-sensitive layer                                                Silver chlorobromide emulsion (1:4           0.23                             (Ag molar ratio) mixture of cubic                                             grains with an average grain size                                             of 0.58 μm and a grain size distribution                                   fluctuation coefficient of 0.90 and                                           cubic grains with an average grain                                            size of 0.45 μm and a grain size                                           distribution fluctuation coefficient                                          of 0.11, each emulsion comprising                                             0.6 mol % AgBr localized thereon)                                             Gelatin                                      1.34                             Cyan coupler (ExC)                           0.32                             Dye image stabilizer (Cpd-6)                 0.17                             Dye image stabilizer (Cpd-7)                 0.40                             Dye image stabilizer (Cpd-8)                 0.04                             Solvent (Solv-6)                             0.15                             6th layer: ultraviolet absorbing layer                                        Gelatin                                      0.53                             Ultraviolet absorbent (UV-1)                 0.16                             Color stain inhibitor (Cpd-5)                0.02                             Solvent (Solv-5)                             0.08                             7th layer: protective layer                                                   Gelatin                                      1.33                             Acryl-modified copolymer of                  0.17                             polyvinyl alcohol (modification                                               degree: 17%)                                                                  Liquid paraffin                              0.03                             __________________________________________________________________________    Yellow Coupler (ExY)                                                          1:1 (molar ratio) mixture of:                                                  ##STR18##                                                                     ##STR19##                                                                     ##STR20##                                                                    Magenta Coupler (ExM)                                                         1:1 (molar ratio) mixture of:                                                  ##STR21##                                                                    and                                                                            ##STR22##                                                                    Cyan Coupler (ExC)                                                            2:4:4 (weight ratio) mixture of:                                               ##STR23##                                                                    R = C.sub.2 H.sub.5 and C.sub.4 H.sub.9                                        ##STR24##                                                                    Dye image stabilizer (Cpd-1)                                                   ##STR25##                                                                    Dye image stabilizer (Cpd-2)                                                   ##STR26##                                                                    Dye image stabilizer (Cpd-3)                                                   ##STR27##                                                                    Dye image stabilizer (Cpd-4)                                                   ##STR28##                                                                    Dye image stabilizer (Cpd-5)                                                   ##STR29##                                                                    Dye image stabilizer (Cpd-6)                                                  2:4:4 (weight ratio) mixture of:                                               ##STR30##                                                                     ##STR31##                                                                     ##STR32##                                                                    Dye image stabilizer (Cpd-7)                                                   ##STR33##                                                                    average molecular weight: 60,000                                              Dye image stabilizer (Cpd-8)                                                   ##STR34##                                                                    Dye image stabilizer (Cpd-9)                                                   ##STR35##                                                                    Ultraviolet absorbent (UV-1)                                                  4:2:4 (weight ratio) mixture of:                                               ##STR36##                                                                     ##STR37##                                                                     ##STR38##                                                                    Solvent (Solv-1)                                                               ##STR39##                                                                    Solvent (Solv-2)                                                              2:1 (volume ratio) mixture of:                                                 ##STR40##                                                                     ##STR41##                                                                    Solvent (Solv-4)                                                               ##STR42##                                                                    Solvent (Solv-5)                                                               ##STR43##                                                                    Solvent (Solv-6)                                                               ##STR44##                                                                           The above mentioned light-sensitive material was imagewise exposed     to light, and then subjected to continuous processing (running test) in       the following steps by means of a paper processing machine until the          replenishment reached twice the tank capacity of the blix bath.               ______________________________________                                        Processing  Temper-           Replenish-                                                                            Tank                                    Step        ature    Time     ment rate                                                                             capacity                                ______________________________________                                        Color development                                                                         35° C.                                                                          45 sec.  109 ml  17 l                                    Blix        35° C.                                                                          45 sec.   61 ml  17 l                                    Rinse 1     35° C.                                                                          30 sec.  --      10 l                                    Rinse 2     35° C.                                                                          30 sec.  --      10 l                                    Rinse 3     35° C.                                                                          30 sec.  300 ml                                          Drying      80° C.                                                                          60 sec.                                                  ______________________________________                                         *Determined per m.sup.2 of lightsensitive material                            *The blix bath was replenished with its replenisher and the solution from     Rinse 1 (121 ml).                                                             *The rinse was effected in a 3stage countercurrent process wherein water      flows backward.                                                          

    ______________________________________                                                           Running                                                                       Solution                                                                              Replenisher                                        ______________________________________                                        Color developer                                                               Water                800    ml     800  ml                                    Ethylenediamine-N,N,N,N-                                                                           3.0    g      3.0  g                                     tetramethylenephosphonic                                                      acid                                                                          Triethanolamine      5.0    g      5.0  g                                     Potassium chloride   3.1    g      --                                         Potassium bromide    0.015  g      --                                         Potassium carbonate  25     g      25   g                                     Hydraziondiacetic acid                                                                             5.0    g      7.0  g                                     N-ethyl-N-(β-methane-                                                                         5.0    g      9.5  g                                     sulfonamideethyl)-3-methyl-                                                   4-aminoaniline sulfate                                                        Fluorescent brightening                                                                            1.0    g      2.5  g                                     agent (WHITEX-4, available                                                    from Sumitomo Chemical Co., Ltd.)                                             Water to make        1,000  ml     1,000                                                                              ml                                    pH adjusted with potassium                                                                         10.05         10.60                                      hydroxide                                                                     Blix solution                                                                 Water                600    ml     600  ml                                    70 wt. % Ammonium    100    ml     245  ml                                    thiosulfate                                                                   or compound of the   0.4    mol    1.0  mol                                   present invention                                                             Ammonium sulfite     45     g      105  g                                     Ferric ammonium ethylene-                                                                          55     g      135  g                                     diaminetetraacetate                                                           Ethylenediaminetetraacetic                                                                         3.0    g      8.0  g                                     acid                                                                          Ammonium bromide     30     g      75   g                                     Nitric acid (67%)    27     g      68   g                                     Water to make        1      l      1    l                                     pH                   5.80          5.60                                       ______________________________________                                    

Rinse Solution (The running solution was used also as replenishmer)

Ion-exchanged water (Ca and Mg concentration: 3 ppm or less each)

The specimen which had been subjected to running processing was thenstored at a temperature of 60° C. and a relative humidity of 70% for 10days. The change in the minimum magenta density (ΔDmin) between beforeand after the heat and humidity test was determined. The specimen wasfurther measured for the amount of silver left on the unexposed portionby means X-ray fluorescence.

Comparative specimens were prepared in the same manner as in Example 1except that the compound of the present invention was replaced byComparative Compounds (A), (B), (C) and (D) in the equimolecular amount,respectively. These comparative specimens were then subjected to thesame tests as described above.

The results are set forth in Table 3.

Table 3 shows that the use of the compound of the present invention asfixing agent can provide excellent results, i.e., excellent desilveringproperties upon rapid processing and little stain after heat andhumidity test.

                  TABLE 3                                                         ______________________________________                                                           Change in minimum                                                    Residual magenta density                                                      amount   (ΔDmin) between                                      Fixing    of silver                                                                              before and after                                           agent     (μg/cm.sup.2)                                                                       thermal test   Remarks                                     ______________________________________                                        Ammonium  0.4      +0.03          Comparative                                 thiosulfate                                                                   Compound A-1                                                                            0.4      +0             Present                                                                       Invention                                   Compound A-2                                                                            0.4      +0             Present                                                                       Invention                                   Compound A-6                                                                            0.3      +0             Present                                                                       Invention                                   Comparative                                                                             1.4      +0.04          Comparative                                 Compound A                                                                    Comparative                                                                             1.5      +0.05          Comparative                                 Compound B                                                                    Comparative                                                                             1.3      +0.04          Comparative                                 Compound C                                                                    Comparative                                                                             1.3      +0.04          Comparative                                 Compound D                                                                    ______________________________________                                    

EXAMPLE 6

Specimens were prepared in the same manner as in Example 5 except thatCompound A-1 was replaced by Compounds A-3, A-5, A-7, A-9, and A-13,respectively, and then subjected to the same tests as in Example 5.

As a result, it was found that the use of the fixing agents of thepresent invention can provide excellent properties as in Example 5.

EXAMPLE 7

The same light-sensitive material as prepared in Example 5 was imagewiseexposed to light, and then subjected to continuous processing (runningtest) in the following steps by means of a paper processing machineuntil the replenishment reached twice the tank capacity of the blixbath.

    ______________________________________                                        Processing                                                                              Temper-            Replenish-                                                                            Tank                                     Step      ature    Time      ment rate*                                                                            capacity                                 ______________________________________                                        Color     39° C.                                                                          45 sec.   70 ml   20 l                                     development                                                                   Blix      35° C.                                                                          45 sec.    60 ml**                                                                              20 l                                     Rinse 1   35° C.                                                                          20 sec.   --      10 l                                     Rinse 2   35° C.                                                                          20 sec.   --      10 l                                     Rinse 3   35° C.                                                                          20 sec.   360 ml  10 l                                     Drying    80° C.                                                                          60 sec.                                                    ______________________________________                                         *Determined per m2 of lightsensitive material The rinse was effected in a     3stage countercurrent process wherein water flows backward.                   *In addition to 60 ml replenishment, the solution from Rinse 1 was            introduced into the blix bath at a flow rate of 120 ml per m.sup.2 of         lightsensitive material.                                                 

    ______________________________________                                                           Running                                                                       Solution                                                                              Replenisher                                        ______________________________________                                        Color developer                                                               Water                700    ml     700  ml                                    Diethylenetriaminepentaacetic                                                                      0.4    g      0.4  g                                     acid                                                                          N,N,N-tetrakis(methylene-                                                                          4.0    g      4.0  g                                     phosphonic acid)                                                              Disodium 1,2-dihydroxybenzene-                                                                     0.5    g      0.5  g                                     4,6-disulfonate                                                               Triethanolamine      12.0   g      12.0 g                                     Potassium chloride   6.5    g      --                                         Potassium bromide    0.03   g      --                                         Potassium carbonate  27.0   g      27.0 g                                     Fluorescent brightening                                                                            1.0    g      3.0  g                                     agent (WHITEX-4, available                                                    from Sumitomo Chemical Co., Ltd.)                                             Sodium sulfite       0.1    g      0.1  g                                     N,N-bis(sulfoethyl)  10.0   g      13.0 g                                     hydroxylamine                                                                 N-ethyl-N-(β-methane-                                                                         5.0    g      11.5 g                                     sulfonamideethyl)-3-                                                          methyl-4-aminoaniline                                                         sulfate                                                                       Water to make        1,000  ml     1,000                                                                              ml                                    pH (25%)             10.10         11.10                                      Blix solution                                                                 Water                600    ml     150  ml                                    700 g/l Ammonium     100    ml     250  ml                                    thiosulfate                                                                   or compound of the   0.47   mol    1.2  mol                                   present invention                                                             Ammonium sulfite     40     g      100  g                                     Ferric ammonium ethylene-                                                                          55     g      135  g                                     diaminetetraacetate                                                           Ethylenediaminetetraacetic                                                                         5      g      12.5 g                                     acid                                                                          Ammonium bromide     40     g      75   g                                     67% Nitric acid      30     g      65   g                                     Water to make        1,000  ml     1,000                                                                              ml                                    pH at 25° C. adjusted with                                                                  5.8           5.6                                        acetic acid and aqueous                                                       ammonia                                                                       ______________________________________                                    

Rinse Solution (The running solution was used also as replenishmer)

Ion-exchanged water (Ca and Mg concentration: 3 ppm or less each)

The specimen which had been subjected to running processing was thenstored at a temperature of 60° C. and a relative humidity of 70% for 10days. The change in the minimum magenta density (ΔDmin) between beforeand after the heat and humidity test was determined. The specimen wasfurther measured for the amount of silver left on the unexposed portionby means of a fluorescent X-ray analyzer.

Comparative specimens were prepared in the same manner as in Example 1except that the compound of the present invention was replaced byComparative Compounds (A), (B), (C) and (D) in the equimolecular amount,respectively. These comparative specimens were then subjected to thesame tests as described above.

The results are set forth in Table 4.

Table 4 shows that the use of the compound of the present invention asfixing agent can provide excellent results, i.e., excellent desilveringproperties upon rapid processing and little stain after heat andhumidity test.

EXAMPLE 8

Specimens were prepared in the same manner as in Example 7 except thatCompound A-1 was replaced by Compounds A-3, A-5, A-7, A-9, A-12, A-14,A-18, A-22, A-29, A-30, A-43, and A-52, respectively, and then subjectedto the same tests as in Example 7.

As a result, it was found that the use of the fixing agents of thepresent invention can provide excellent properties as in Example 7.

                  TABLE 4                                                         ______________________________________                                                           Change in minimum                                                    Residual magenta density                                                      amount   (ΔDmin) between                                      Fixing    of silver                                                                              before and after                                           agent     (μg/cm.sup.2)                                                                       thermal test  Remarks                                      ______________________________________                                        Ammonium  0.4      +0.04         Comparative                                  thiosulfate                                                                   Compound A-1                                                                            0.5      ±0         Present                                                                       Invention                                    Compound A-2                                                                            0.4      ±0         Present                                                                       Invention                                    Compound A-6                                                                            0.3      ±0         Present                                                                       Invention                                    Comparative                                                                             1.5      +0.05         Comparative                                  Compound A                                                                    Comparative                                                                             1.7      +0.06         Comparative                                  Compound B                                                                    Comparative                                                                             1.4      +0.05         Comparative                                  Compound C                                                                    Comparative                                                                             1.5      +0.05         Comparative                                  Compound D                                                                    ______________________________________                                    

EXAMPLE 9 Preparation of Emulsion

30 g of gelatin and 6 g of potassium bromide were added to 1 l of water.The solution was kept at a temperature of 60° C. An aqueous solution of5 g of silver nitrate and an aqueous solution of potassium bromidecontaining 0.15 g of potassium iodide were added to the solution withstirring by a double jet process in 1 minute. Further, an aqueoussolution of 145 g of silver nitrate and an aqueous solution of potassiumbromide containing 4.2 g of potassium iodide were added to the system bya double jet process. The flow rate was accelerated such that the flowrate at the end of the addition became 5 times that at the beginning ofthe addition. After the completion of the addition, soluble salts wereremoved at a temperature of 35° C. by a sedimentation process. Theemulsion was then heated to a temperature of 40° C. 75 g of gelatin wasthen added to the emulsion so that the pH value thereof was adjusted to6.7. The emulsion thus obtained comprised tabular grains with a diameterof 0.98 μm as calculated in terms of projected area, an averagethickness of 0.138 μm and a silver iodide content of 3 mol %. Theemulsion was then subjected to chemical sensitization, i.e., goldsensitization and sulfur sensitization in combination.

Preparation of Photographic Material

As surface protective layer component there was used an aqueous solutionof gelatin containing a polyacrylamide having an average molecularweight of 8,000, sodium polystyrenesulfonate, finely dividedpolymethylmethacrylate grains (average grain size: 3.0 μm), polyethyleneoxide, and film hardener.

To the emulsion were added sodium salt ofanhydro-5,5'-dichloro-9-ethyl-3,3'-di(3-sulfopropyl)oxacarbocyaninehydroxide and potassium iodide in amounts of 500 mg/molsilver and 200 mg/mol silver, respectively, as sensitizing dyes. To thesystem were further added 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene,2,6-bis(hydroxyamino)-4-diethylamino-1,3,5-triazine and nitron asstabilizers, trimethylpropane as dry fog inhibitor, a coating aid, and afilm hardening aid. The coating solution thus prepared was coated onboth surfaces of a polyethylene terephthalate support simultaneouslywith the surface protective layer coating solution, and then dried toprepare a photographic material. The coated amount of silver on onesurface of the photographic material was g/m². The photographic materialexhibited a percent swelling of 180% as defined above.

The photographic material was exposed to X-ray by 50% , and thenprocessed with the following developer, fixing solution and rinsesolution.

    ______________________________________                                        Processing step                                                                                  Temper-  Replenish-                                                                              Tank                                    Step      Time     ature    ment rate capacity                                ______________________________________                                        Development                                                                             13.7 sec.                                                                              35° C.                                                                          20 ml (+10 ml                                                                           15 l                                                                diluent)                                          Fixing    12.5 sec.                                                                              32° C.                                                                          10 ml (+30 ml                                                                           15 l                                                                diluent)                                          Rinse      6.2 sec.                                                                              20° C.                                                                          500 ml    10 l                                    Squeeze roller washing tank 200 ml                                            ______________________________________                                         *Replenishment rate: per quater size (10 inch × 12 inch) sheet of       lightsensitive material                                                  

    ______________________________________                                                           Running                                                                       Solution                                                                              Replenisher                                        ______________________________________                                        Color developer                                                               Potassium hydroxide  24     g      60   g                                     Sodium sulfite       40     g      100  g                                     Potassium sulfite    50     g      125  g                                     Diethylenetriaminepentaacetic                                                                      2.4    g      6    g                                     acid                                                                          Boric acid           10     g      25   g                                     Hydroquinone         35     g      87.5 g                                     Diethylene glycol    11.2   g      28   g                                     4-Hydroxymethyl-4-methyl-                                                                          2.5    g      6.25 g                                     1-phenyl-3-pyrazolidone                                                       5-Methylbenzotriazole                                                                              0.06   g      0.15 g                                     pH                   10.05         11.00                                      Fixing solution                                                               Ammonium thiosulfate 140    g      560  g                                     or compound of the present                                                                         1      mol    4    mol                                   invention                                                                     Sodium sulfite       15     g      60   g                                     Disodium ethylenediamine-                                                                          0.025  g      0.1  g                                     tetraacetate dihydrate                                                        Sodium hydroxide     6      g      24   g                                     pH                   5.5           5.10                                       Rinse solution                                                                Disodium ethylenediamine-                                                                          0.5    g      0.5  g                                     tetraacetate dihydrate                                                        ______________________________________                                    

The specimen was then subjected to running processing at a rate of 50quarter size sheets a day (percentage development per one sheet of film:40%) until the accummulated replenishment of the fixing solution reached3 times the tank capacity of the running solution.

The circulated amount of the developer was set to 20 l/min. while thelight-sensitive material was developed and 6 l/min. while thelight-sensitive material was ready for development.

The specimen which had been subjected to running processing was thensubjected to fixing for 10.5 seconds and 11.5 seconds.

The specimens thus processed were then measured for amount of silverleft on the unexposed portion by means of a fluorescent X-ray analyzer.

Another batch of the specimen which had been subjected to runningprocessing was stored at a temperature of 60° C. and a relative humidityof 70% for 10 days. The change in the minimum density (ΔDmin) betweenbefore and after storage was determined.

Comparative specimens were prepared in the same manner as in Specimen101 except that the compound of the present invention was replaced byComparative Compounds (A), (B), (C) and (D) in the equimolecular amount,respectively. These comparative specimens were then subjected to thesame tests as described above.

Further, the light-sensitive material B was subjected to the same testsas described above.

The results are set forth in Table 5.

Table 5 shows that the use of the compound of the present invention asfixing agent can provide excellent results, i.e., excellent desilveringproperties upon rapid processing and little stain after heat andhumidity test.

                                      TABLE 5                                     __________________________________________________________________________                       Change in minimum                                                  Residual amount                                                                          magenta density                                                    of silver (μg/cm.sup.2)                                                               (ΔDmin) between                                      Fixing  10.5-sec.                                                                          11.5-sec.                                                                           before and after                                           agent   fixing                                                                             fixing                                                                              thermal test                                                                            Remarks                                          __________________________________________________________________________    Ammonium                                                                              10.3 3.2   +0.24     Comparative                                      thiosulfate                                                                   Compound A-1                                                                          1.0  0.7   +0.07     Present                                                                       Invention                                        Compound A-2                                                                          1.1  0.7   +0.0      Present                                                                       Invention                                        Compound A-6                                                                          1.1  0.7   +0.08     Present                                                                       Invention                                        Comparative                                                                           5.0  0.8   +0.29     Comparative                                      Compound A                                                                    Comparative                                                                           3.9  0.9   +0.25     Comparative                                      Compound B                                                                    Comparative                                                                           3.8  0.8   +0.22     Comparative                                      Compound C                                                                    Comparative                                                                           3.9  0.8   +0.24     Comparative                                      Compound D                                                                    __________________________________________________________________________

EXAMPLE 10

Specimens were prepared in the same manner as in Example 9 except thatCompound A-1 was replaced by Compounds A-3, A-5, A-7, A-9, and A-14,respectively, and then subjected to the same tests as in Example 9.

As a result, it was found that the use of the fixing agents of thepresent invention can provide excellent properties as in Example 9,i.e., little thermostain after heat and humidity test and excellentdesilvering properties (fixing properties) upon rapid processing.

EXAMPLE 11

(1) Preparation of Tabular Grains

Preparation of Emulsion

5 g of potassium bromide, 0.05 g of potassium iodide, 30 g of gelatinand 2.5 cc of a 5% aqueous solution of thioether HO(CH₂)₂ S(CH₂)₂S(CH₂)₂ OH were added to 1 l of water. The solution was kept at atemperature of 73° C. An aqueous solution of 8.33 g of silver nitrateand an aqueous solution of 5.94 g of potassium bromide and 0.726 g ofpotassium iodide were added to the solution with stirring by a doublejet process in 45 seconds. 2.5 g of potassium bromide was then added tothe system. An aqueous solution of 8.33 g of silver nitrate was thenadded to the system in 26 minutes in such a manner that the flow rate atthe end of the addition became twice that at the beginning of theaddition.

Thereafter, the emulsion was subjected to physical ripening with 20 ccof a 25% ammonia solution and 10 cc of a 50% NH₄ NO₃ solution for 20minutes. The emulsion was then neutralized with 240 cc of 1N sulfuricacid. Subsequently, an aqueous solution of 153.34 g of silver nitrateand an aqueous solution of potassium bromide were added to the emulsionby a controlled double jet process in 40 minutes while the potentialthereof was kept at a pAg value of 8.2. The flow rate was acceleratedsuch that the flow rate at the end of the addition became 9 times thatat the beginning of the addition. After the completion of the addition,15 cc of a 2N solution of potassium thiocyanate was added to theemulsion. Further, 25 cc of a 1% aqueous solution of potassium iodidewas added to the emulsion in 30 seconds. The emulsion was then cooled toa temperature of 35° C. so that soluble salts were removed bysedimentation. The emulsion was then heated to a temperature of 40° C.30 g of gelatin and 2 g of phenol were then added to the emulsion. Theemulsion was then adjusted with caustic soda and potassium bromide to apH value of 6.40 and a pAg value of 8.10.

The emulsion was then heated to a temperature of 56° C. 600 mg of asensitizing dye having the following structure and 150 mg of astabilizer having the following structure were added to the emulsion.After 10 minutes, 2.4 mg of hydrate of sodium thiosulfate, 140 mg ofpotassium thiocyanate and 2.1 mg of chloroauric acid were added 'to theemulsion. After 80 minutes, the emulsion was quenched and solidified toprepare the desired emulsion. The emulsion thus obtained comprisedgrains wherein 98% of all grains have as aspect ratio of 3 or more ascalculated in terms of projected area. All grains having an aspect ratioof 2 or more had an average diameter of 1.4 μm as calculated in terms ofprojected area, a standard deviation in diameter distribution of 22%, anaverage thickness of 0.187 μm and an aspect ratio of 7.5. ##STR45##

Preparation of Emulsion Coating Solution

To the emulsion was added the following chemicals (per mol of silverhalide):

    ______________________________________                                        Gelatin            Added amount adjusted                                                         such that Ag/(gelatin +                                                       polymer) weight                                                               ratio was 1.10                                             Water-soluble polyester                                                                          20 wt. % based on                                                             gelatin                                                    Polymer latex (poly(ethyl-                                                                       25.0 g                                                     acrylate/methacrylic acid =                                                   97/3)                                                                         Film hardener                                                                 1,2-Bis(vinylsulfonyl-                                                                           8 m mol/100 g of                                           acetamide)ethane   gelatin in emulsion                                                           layer on surface                                                              protective layer                                           Phenoxyethanol     2 g                                                        2,6-Bis(hydroxyamino)-4-                                                                         80 mg                                                      diethylamino-1,3,5-                                                           triazine                                                                      Sodium polyacrylate                                                                              4.0 g                                                      (average molecular                                                            weight: 41,000)                                                               Potassium polystyrene-                                                                           1.0 g                                                      sulfonate (average                                                            molecular weight: 600,000)                                                    ______________________________________                                    

Preparation of Light-Sensitive Material A

The coating solution thus obtained was then coated simultaneously with asurface protective layer coating solution on a 175-μm thick transparentPET support.

The sum of the coated amount of silver on both surfaces was 3.2 g/m².

The surface protective layer coating solution was prepared in such amanner that the coated amount of each component was as set forth below.

    ______________________________________                                        Component of surface protective layer                                                                  Coated amount                                        ______________________________________                                        Gelatin                  1.15    g/m.sup.2                                    Polyacrylamide (average molecular                                                                      0.25    g/m.sup.2                                    weight: 45,000)                                                               Sodium polyacrylate (average                                                                           0.02    g/m.sup.2                                    molecular weight: 400,000)                                                    Sodium salt of p-t-octylphenoxydi-                                                                     0.02    g/m.sup.2                                    glycerylbutylsulfonate                                                        Polyoxyethylene ethyl ether                                                                            0.035   g/m.sup.2                                    (polymerization degree: 10)                                                   Polyoxyethylene(polymerization                                                                         0.01    g/m.sup.2                                    degree: 10)-polyoxyglyceryl                                                   (polymerization degree: 3)-p-                                                 octylphenoxyether                                                             2-Chlorohydroquinone     0.046   g/m.sup.2                                    C.sub.8 F.sub.17 SO.sub.3 K                                                                            0.003   g/m.sup.2                                     ##STR46##               0.001   g/m.sup.2                                     ##STR47##               0.003   g/m.sup.2                                    Proxel                   0.001   g/m.sup.2                                    Polymethyl methacrylate  0.025   g/m.sup.2                                    (average grain diameter: 3.5 μm)                                           Poly(methylmethacrylate/ 0.020   g/m.sup.2                                    methacrylate) (molar ratio:                                                   7:3; average grain                                                            diameter: 2.5 μm)                                                          ______________________________________                                    

(2) Preparation of Potato-Shaped Grains

Preparation of Emulsion

20 g of gelatin, 30 g of potassium bromide, and 3.91 g of potassiumiodide were added to 900 cc of water. The solution was kept at atemperature of 48° C. 35 g of silver nitrate was added to the solutionwith stirring in the form of aqueous solution in 4 minutes.

Ammonia silver nitrate (165 g of silver nitrate) was added to the systemsimultaneously with an aqueous solution of potassium bromide by a doublejet process in 5 minutes. After the completion of the addition, solublesalts were removed from the system at a temperature of 35° C. bysedimentation. The system was then heated to a temperature of 40° C. 100g of gelatin was further added to the system so that the pH valuethereof was adjusted to 6.7. The resulting emulsion comprisedpotato-shaped grains. The average grain diameter of grains having thesame volume was 0.82 μm. The silver iodide content of the grains was 2mol %. The emulsion was then subjected to chemical sensitization, i.e.,gold sensitization and sulfur sensitization in combination.

Preparation of Light-Sensitive Material B

As surface protective layer component there was used an aqueous solutionof gelatin containing a polyacrylamide having an average molecularweight of 8,000, sodium polystyrenesulfonate, finely dividedpolymethylmethacrylate grains (average grain size: 3.0 μm), polyethyleneoxide, and film hardener.

To the emulsion were added sodium salt ofanhydro-5,5'-dichloro-9-ethyl-3,3'-di(3-sulfopropyl)oxacarbocyaninehydroxide and potassium iodide in amounts of 500 mg/molsilver and 200 mg/mol silver, respectively, as sensitizing dyes.

To the system were further added 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazineand nitron as stabilizers, trimethylpropane as dry fog inhibitor, acoating aid, and a film harder. The coating solution thus prepared wascoated on both surfaces of a polyethylene terephthalate supportsimultaneously with the surface protective layer coating solution, andthen dried to prepare Light--Sensitive Material B. The sum of the coatedamount of silver on both surfaces of the support was 6.4 g/m².

    ______________________________________                                        Development                                                                   Preparation of concentrated solution                                          ______________________________________                                        <Developer>                                                                   Part A                                                                        Potassium hydroxide     330    g                                              Potassium sulfite       630    g                                              Sodium sulfite          240    g                                              Potassium carbonate     90     g                                              Boric acid              45     g                                              Diethylene glycol       180    g                                              Diethylenetriaminepentaacetic                                                                         30     g                                              acid                                                                          1-(Diethylaminoethyl)-5-                                                                              0.75   g                                              mercaptotetrazole                                                             Hydroquinone            450    g                                              Water to make           4,125  ml                                             Part B                                                                        Diethylene glycol       525    g                                              Glacial acetic acid     102.6  g                                              5-Nitroindazole         3.75   g                                              1-Phenyl-3-pyrazolidone 34.5   g                                              Water to make           750    ml                                             Part C                                                                        Glutaraldehyde (50 wt/wt %)                                                                           150    ml                                             Potassium methabisulfite                                                                              150    ml                                             Potassium bromide       15     g                                              Water to make           750    ml                                             <Fixing Solution>                                                             Ammonium thiosulfate    200    ml                                             (70 wtvol. %)                                                                 or compound of the present                                                                            0.95   mol                                            invention                                                                     Disodium ethylenediamine-                                                                             0.03   g                                              tetraacetate dihydrate                                                        Sodium thiosulfate pentahydrate                                                                       10     g                                              Sodium sulfite          20     g                                              Boric acid              4      g                                              1-(N,N-dimethylamino)-ethyl-5-                                                                        1      g                                              mercaptotetrazole                                                             Tartaric acid           3.2    g                                              Glacial acetic acid     45     g                                              Sodium hydroxide        15     g                                              36 N Sulfuric acid      3.9    g                                              Aluminum sulfate        10     g                                              Water to make           400    ml                                             pH                      4.68                                                  ______________________________________                                    

Preparation of Processing Solution

These parts of the concentrated developer thus obtained were eachcharged into the respective polyethylene vessels which were connected toone point.

The concentrated fixing solution was similarly charged into apolyethylene vessel.

The concentrated developer was then stored in the vessel at atemperature of 50° C. for 3 months for later preparation as developer.

The developer and fixing solution were then charged into the developmenttank and fixing tank of an automatic developing machine in the followingproportions by means of a constant delivery pump.

    ______________________________________                                        Developer I                                                                   Agent A                  55 ml                                                Agent B                  10 ml                                                Agent C                  10 ml                                                Water                   125 ml                                                pH                       10.50                                                Fixing Solution                                                               Concentration solution   80 ml                                                Water                   120 ml                                                pH                       4.64                                                 ______________________________________                                    

The rinse tank was filled with tap water. Four nonwovon bags containing50 g of a silver-releasing agent which comprises a soluble glassconsisting of Na₂ O (10 wt %), B₂ O₅ (65 wt %) and SiO₂ (25 wt %)containing 1.7 wt % of Ag₂ O were sent to the bottom of the rinse tank.

Structure of Automatic Developing Machine

There was used an automatic developing machine having the followingstructure:

    __________________________________________________________________________                 Process-                                                                             Length                                                                              Process-                                                                           Process-                                              Tank  ing    of path                                                                             ing 1                                                                              ing 2                                          Step   capacity                                                                            temp.  processed                                                                           time time                                           __________________________________________________________________________    Development                                                                          15 l  35° C. (for                                                                   613 mm                                                                              13.3 sec.                                                                          24.5 sec.                                                   Processing 1)                                                                 32° C. (for                                                            Processing 2)                                                    (Ratio of liquid surface to tank capacity = 35 cm.sup.2 /l)                   Fixing 15 l  32° C.                                                                        541 mm                                                                              11.7 sec.                                                                          21.6 sec.                                      Fixing 13 l  17° C.                                                                        305 mm                                                                               5.7 sec.                                                                          10.5 sec.                                                   running                                                                       water                                                            Squeeze                    6.6 sec.                                                                          12.2 sec.                                      Drying       58° C.                                                                        368 mm                                                                               8.0 sec.                                                                          14.7 sec.                                      Total               1,827 mm                                                                            45.3 sec.                                                                          83.6 sec.                                      __________________________________________________________________________

Processing Specimens 102 to 113

Light-Sensitive Material A was exposed to X-ray by 50%, and thensubjected to development with the above mentioned processing solutionsfor the processing time or processing 2 time by means of the abovementioned automatic developing machine with the replenishment rate ofdeveloper and fixing solution controlled to 45 ml and 30 ml per quatersize sheet (10×12 inch), respectively.

The flow rate of the rinse solution was 5 l/min. for Processing 2 and 10l/min. for Processing 1. A solenoid valve was opened in synchronous withthe processing of the light-sensitive material so that the rinsesolution was supplied (about 1 l/quater size sheet). At the end of aday's operation, a solenoid valve was automatically opened to remove therinse solution from the tank. The crossover rollers between developmentand fixing and between fixing and rinse were provided with an apparatuswhich automatically sprays wash water thereto for cleaning (method asdescribed in Japanese Patent Application No. 61-131338).

2,000 quater size sheets of the specimen were processed at the sameposition (running test). The specimen which had been subjected torunning test was then stored at a temperature of 60° C. and a relativehumidity of 70% for 10 days. The change in the minimum density (ΔDmin)between before and after storage was determined. The specimen wasfurther processed with the fixing time slightly reduced. The specimenwas measured for the amount of silver left on the unexposed portion.

Comparative specimens were prepared in the same manner as in Example 1except that the compound of the present invention was replaced byComparative Compounds (A), (B), (C) and (D) in the equimolecular amount,respectively, and then subjected to the same tests as described above.

Further, Light-Sensitive Material B was subjected to the same tests asdescribed above.

The results are set forth in Table 6.

Table 6 shows that the use of the compound of the present invention asfixing agent can provide excellent results, i.e., excellent desilveringproperties upon rapid processing and little stain after heat andhumidity test.

                                      TABLE 6                                     __________________________________________________________________________    (Light-Sensitive Material A; Processing 1)                                                       Change in minimum                                                             magenta density                                                               (ΔDmin) between                                      Fixing  Residual amount                                                                          before and after                                           agent   of silver (μg/cm.sup.2)                                                               thermal test                                                                            Remarks                                          __________________________________________________________________________            10.9-sec.                                                                          11.7-sec.                                                                fixing                                                                             fixing                                                           Ammonium                                                                              6.0  0.9   +0.25     Comparative                                      thiosulfate                                                                   Compound A-1                                                                          0.9  0.7   +0.07     Present                                                                       Invention                                        Compound A-2                                                                          1.0  0.7   +0.08     Present                                                                       Invention                                        Compound A-6                                                                          1.0  0.7   +0.08     Present                                                                       Invention                                        Comparative                                                                           3.6  0.8   +0.30     Comparative                                      Compound A                                                                    Comparative                                                                           3.7  0.9   +0.26     Comparative                                      Compound B                                                                    Comparative                                                                           3.4  0.8   +0.22     Comparative                                      Compound C                                                                    Comparative                                                                           3.4  0.9   +0.24     Comparative                                      Compound D                                                                            20.8-sec.                                                                          21.6-sec.                                                                fixing                                                                             fixing                                                           Ammonium                                                                              5.5  0.8   +0.20     Comparative                                      thiosulfate                                                                   Compound A-1                                                                          0.8  0.6   +0.06     Present                                                                       Invention                                        Compound A-2                                                                          0.9  0.6   +0.07     Present                                                                       Invention                                        Compound A-6                                                                          0.8  0.6   +0.07     Present                                                                       Invention                                        Comparative                                                                           3.1  0.7   +0.25     Comparative                                      Compound A                                                                    Comparative                                                                           3.0  0.8   +0.21     Comparative                                      Compound B                                                                    Comparative                                                                           2.9  0.7   +0.19     Comparative                                      Compound C                                                                            10.9-sec.                                                                          11.7-sec.                                                                fixing                                                                             fixing                                                           Ammonium                                                                              5.8  0.8   +0.24     Comparative                                      thiosuflate                                                                   Compound A-1                                                                          0.7  0.6   +0.07     Present                                                                       Invention                                        Compound A-2                                                                          0.8  0.6   +0.07     Present                                                                       Invention                                        Compound A-6                                                                          0.8  0.6   +0.08     Present                                                                       Invention                                        Comparative                                                                           3.2  0.7   +0.30     Comparative                                      Compound A                                                                    Comparative                                                                           3.3  0.7   +0.26     Comparative                                      Compound B                                                                    Comparative                                                                           3.0  0.7   +0.22     Comparative                                      Compound C                                                                            20.8-sec.                                                                          21.6-sec.                                                                fixing                                                                             fixing                                                           Ammonium                                                                              5.5  0.7   +0.21     Comparative                                      thiosulfate                                                                   Compound A-1                                                                          0.7  0.6   +0.06     Present                                                                       Invention                                        Compound A-2                                                                          0.7  0.6   +0.06     Present                                                                       Invention                                        Compound A-6                                                                          0.9  0.5   +0.07     Present                                                                       Invention                                        Comparative                                                                           3.1  0.6   +0.25     Comparative                                      Compound A                                                                    Comparative                                                                           3.1  0.7   +0.23     Comparative                                      Compound B                                                                    Comparative                                                                           2.9  0.6   +0.20     Comparative                                      Compound C                                                                    __________________________________________________________________________

EXAMPLE 12

Specimens were prepared in the same manner as in Example 11 except thatCompound A-1 was replaced by Compounds A-3, A-4, A-5, A-7, A-8, A-9,A-13, A-17, A-20, A-24, A-31, and A-52, respectively, and then subjectedto the same tests as in Example 11.

As a result, it was found that the use of the fixing agents of thepresent invention can provide excellent properties as in Example 11,i.e., little thermostain after heat and humidity test and excellentdesilvering properties upon rapid processing.

EXAMPLE 13 Preparation of Light-Sensitive Emulsion Layer

An aqueous solution of silver nitrate and an aqueous solution containingpotassium iodide and potassium bromide were simultaneously added to anaqueous solution of gelatin which had been kept at a temperature of 50°C. in the presence of iridium (III) hexacholoride in an amount of 4×10⁻⁷per mol of silver and ammonia while the pAg value of the system was keptat 7.8. As a result, a monodisperse emulsion of cubic grains with anaverage grain size of 0.28μ and an average silver iodide content of 0.3mol % was obtained. The emulsion was then subjected to desalting by aflocculation method. Inactive gelatin was then added to the emulsion inan amount of 40 g per mol of silver.5,5'-Dichloro-9-ethyl-3,3'-bis(3-sulfapropyl)oxacarbocyanine assensitizing dye and a potassium iodide solution (10⁻³ mol per molsilver) were added to the emulsion. The emulsion was then aged for 15minutes, and cooled.

Coating of Light-Sensitive Emulsion Layer

The emulsion was re-dissolved. To the emulsion was added the followinghydrazine derivative at a temperature of 40° C: ##STR48## To theemulsion were further added 5-methylbenztriazole,4-hydroxy-1,3,3a,7-tetrazaindene, a compound of the general formula (i)set forth below, a compound of the general formula (ii) set forth below,polyethylene acrylate in an amount of 30 wt % based on gelatin, and acompound of the general formula (iii) set forth below as gelatinhardener. The coating solution thus obtained was then coated on a 150-μthick polyethylene terephthalate film having a subbing layer (0.5μ) madeof a vinylidene chloride copolymer in an amount such that the coatedamount of silver reached 3.4 g/m². ##STR49##

Coating of Protective Layer

As protective layer components there were coated gelatin in an amount of1.5 g/m², polymethyl methacrylate grains (average grain diameter: 2.5μ)in an amount of 0.3 g/m², and finely divided AgCl grains prepared as setforth below in an amount of 0.3 g/m² as calculated in terms of silverwith the aid of the following surface active agents: ##STR50##

These specimens were then cut into large full size sheets (50.8 cm/61.0cm). These specimens were subjected to 50% blackening exposure totungsten light at 3,200° K. 200 sheets of these specimens were thenprocessed in the following processing steps:

    ______________________________________                                        Processing step                                                                        Processing  Processing Replenishment                                 Step     time        temperature                                                                              rate                                          ______________________________________                                        Development                                                                            30 sec.     34° C.                                                                            240 ml                                        Fixing   30 sec.     34° C.                                                                            390 ml                                        Rinse    30 sec.     20° C.                                                                            2 l                                           ______________________________________                                    

The replenishment rate was determined per m2 of light-sensitivematerial.

    ______________________________________                                        Developer (running solution = replenisher)                                    Hydroquinone             50.0    g                                            N-methyl-p-aminophenol   0.3     g                                            Sodium hydroxide         18.0    g                                            Boric acid               20.0    g                                            Potassium sulfite        110.0   g                                            Disodium ethylenediamine-                                                                              1.0     g                                            tetraacetate                                                                  Potassium bromide        10.0    g                                            5-Methylbenzotriazole    0.4     g                                            5-Mercaptobenzimidazole-5-                                                                             0.3     g                                            sulfonic acid                                                                 Sodium 3-(5-mercaptotetrazole)                                                                         0.2     g                                            benzenesulfonate                                                              6-Dimethylamino-1-hexanol                                                                              4.0     g                                            Sodium p-toluenesulfonate                                                                              15.0    g                                            5-Sulfosalicylic acid    30.0    g                                            Water to make            1       l                                            Potassium hydroxide to make pH                                                                         11.7                                                 Fixing solution (running solution = replenisher)                              Ammonium thiosulfate     190.0   g                                            or compound of the present                                                                             1       mol                                          invention                                                                     Sodium sulfite           22.0    g                                            Disodium ethylenediamine-                                                                              0.1     g                                            tetraacetate                                                                  Tartaric acid            3.0     g                                            27% Aqueous ammonia      10.0    g                                            90% Acetic acid          30.0    g                                            27% Aluminum sulfate     35.0    g                                            Water to make            1       l                                            Sodium hydroxide to make pH                                                                            4.8                                                  ______________________________________                                    

The specimen which had been just subjected to the sequential runningtest was then stored at a temperature of 60° C. and a relative humidityof 70% for days. The change in the minimum density (ΔDmin) betweenbefore and after storage Was determined.

The specimen was further processed with the fixing time altered to 25seconds and 30 seconds. The specimen was measured for the amount ofsilver left on the unexposed portion.

Comparative specimens were prepared in the same manner as in Example 1except that the compound of the present invention was replaced byComparative Compounds (A), (B), (C) and (D) in the equimolecular amount,respectively, and then subjected to the same tests as described above.

The results are set forth in Table 7.

Table 7 shows that the use of the compound of the present invention asfixing agent can provide excellent results, i.e., excellent desilveringproperties upon rapid processing and little stain after heat andhumidity test.

                                      TABLE 7                                     __________________________________________________________________________                       Change in minimum                                                   Residual amount                                                                         magenta density                                                     of silver (μg/cm.sup.2)                                                              (ΔDmin) between                                      Fixing   25 sec.                                                                            30 sec.                                                                            before and after                                           agent    fixing                                                                             fixing                                                                             thermal test                                                                            Remarks                                          __________________________________________________________________________    Ammonium 5.0  0.6  +0.20     Comparative                                      thiosulfate                                                                   Compound A-1                                                                           0.6  0.5  +0.06     Present                                                                       Invention                                        Compound A-2                                                                           0.6  0.5  +0.07     Present                                                                       Invention                                        Compound A-6                                                                           0.6  0.6  +0.07     Present                                                                       Invention                                        Comparative                                                                            2.0  0.6  +0.26     Comparative                                      Compound A                                                                    Comparative                                                                            2.2  0.5  +0.24     Comparative                                      Compound B                                                                    Comparative                                                                            1.8  0.6  +0.20     Comparative                                      Compound C                                                                    Comparative                                                                            1.9  0.6  +0.23     Comparative                                      Compound D                                                                    __________________________________________________________________________

EXAMPLE 14

Specimens were prepared in the same manner as in Example 13 except thatCompound A-1 was replaced by Compounds A-3, A-4, A-5, A-7, A-9, A-14,A-18, A-22, A-24, A-30, A-31, A-39, A-43, and A-52, respectively, andthen subjected to the same Zests as in Example 13.

As a result, it was found that the use of the fixing agents of thepresent invention can provide excellent properties as in Example 13,i.e., little thermostain after heat and humidity test and excellentdesilvering properties upon rapid processing.

EXAMPLE 15

Silver halide grains were precipitated by a double jet process. Theemulsion was then subjected to physical ripening and desilveringprocesses. The emulsion was further subjected to chemical ripening toobtain a silver chloroiodobromide emulsion (bromine content: 30 mol %;iodine content: 0.1 mol %). The emulsion comprised silver halide grainswith an average diameter of 0.3 μm. The emulsion contained silver halidein an amount of 0.6 mol per kg.

1 kg of the emulsion was weighed out. The emulsion was then heated to atemperature of 40° C. so that it was dissolved. A methanol solution of asensitizing dye was added to the emulsion. Further, an aqueous solutionof sodium bromide was added to the emulsion in a predetermined amount.25 ml of a 1.0 wt % methanol solution of disodium4,4'-bis[4,6-di(benzothiazolyl-2-thio)pyrimidin-2-ylamino]stilbene-2,2'-disulfonatewas added to the emulsion. Further, 30 ml of a 1.0 wt % aqueous solutionof sodium 1-hydroxy-3,5-dichlorotriazine was added to the emulsion.Further, 40 ml of a 1.0 wt % aqueous solution of sodiumdodecylbenzenesulfonate was added to the emulsion. The emulsion was thenstirred. The finished emulsion was then coated on a cellulose triacetatefilm base to a dried thickness of 5 μm, and dried to obtain alight-sensitive material specimen. The film specimen was then exposed tolight through an optical wedge by means of a sensitometer having a lightsource with a color temperature of 2,666° K. The light source wascovered with a dark red filter (SC-66, available from Fuji Photo Film.,Co., Ltd.). After exposure, the specimen was subjected to continuousprocessing until the replenishment rate reached 3 times the tankcapacity of the developer tank.

    ______________________________________                                        Processing step                                                                                 Temper-    Replenish-                                                                            Tank                                     Step      Time    ature      ment rate*                                                                            capacity                                 ______________________________________                                        Development                                                                             20 sec. 38° C.                                                                            320 ml  18 l                                     Fixing    20 sec. 38° C.                                                                            320 ml  18 l                                     Rinse     20 sec. 20° C.                                                                            2 l     18 l                                     ______________________________________                                         *per m.sup.2 of lightsensitive material                                  

    ______________________________________                                        (Developer) running solution = replenisher                                    Methol                    0.31   g                                            Sodium sulfite anhydride  39.6   g                                            Hydroquinone              6.0    g                                            Sodium carbonate anhydride                                                                              18.7   g                                            Potassium bromide         0.86   g                                            Citric acid               0.68   g                                            Potassium metabisulfite   1.5    l                                            Water to make             1      l                                            (Fixing solution) running solution = replenisher                              Ammonium thiosulfate      200    ml                                           or compound of the present                                                                              1      mol                                          invention                                                                     Sodium hydrogensulfite    12.0   g                                            Disodium ethylenediamine- 0.1    g                                            tetraacetate                                                                  Tartaric acid             3.0    g                                            27% Aqueous ammonia       7.0    g                                            90% Acetic acid           20.0   g                                            27% Aluminum sulfate      35.0   g                                            Water to make             1      l                                            Sodium hydroxide to make pH                                                                             4.2                                                 ______________________________________                                    

The specimen which had been just subjected to the sequential runningtest was then stored at a temperature of 60° C. and a relative humidityof 70% for days. The change in the minimum density (ΔDmin) betweenbefore and after storage was determined by using a P type densitometermanufactured by Fuji Photo Film Co., Ltd.

The specimen was further processed with the fixing time altered to 16seconds and 20 seconds. The specimen was measured for the amount ofsilver left on the unexposed portion.

Comparative specimens were prepared in the same manner as in Example 1except that the compound of the present invention was replaced byComparative Compounds (A), (B), (C) and (D) in the equimolecular amount,respectively, and then subjected to the same tests as described above.

The results are set forth in Table 8.

Table 8 shows that the use of the compound of the present invention asfixing agent can provide excellent results, i.e., excellent desilveringproperties upon rapid processing and little stain after heat andhumidity test.

                                      TABLE 8                                     __________________________________________________________________________                       Change in minimum                                                   Residual amount                                                                         magenta density                                                     of silver (μg/cm.sup.2)                                                              (ΔDmin) between                                               16 sec.                                                                            20 sec.                                                                            before and after                                           Fixing agent                                                                           fixing                                                                             fixing                                                                             thermal test                                                                            Remarks                                          __________________________________________________________________________    Ammonium 4.0  0.5  +0.20     Comparative                                      thiosulfate                                                                   Compound A-1                                                                           0.6  0.5  +0.07     Present                                                                       Invention                                        Compound A-2                                                                           0.7  0.6  +0.08     Present                                                                       Invention                                        Compound A-6                                                                           0.7  0.5  +0.08     Present                                                                       Invention                                        Comparative                                                                            2.0  0.5  +0.26     Comparative                                      Compound A                                                                    Comparative                                                                            2.4  0.6  +0.23     Comparative                                      Compound B                                                                    Comparative                                                                            1.9  0.5  +0.19     Comparative                                      Compound C                                                                    Comparative                                                                            1.9  0.6  +0.20     Comparative                                      Compound D                                                                    __________________________________________________________________________

EXAMPLE 16

Specimens were prepared in the same manner as in Example 15 except thatCompound A-1 was replaced by Compounds A-3, A-4, A-5, A-7, A-8, A-9,A-14, A-20, A-22, A-30, A-39, A-43, A-45, and A-52, respectively, andthen subjected to the same tests as in Example 15.

As a result, it was found that the use of the fixing agents of thepresent invention can provide excellent properties as in Example 15,i.e., little thermostain after heat and humidity test and excellentdesilvering properties (fixing properties) upon rapid processing.

EXAMPLE 17

A light-sensitive material (color reversal film) prepared in the samemanner as in Specimen 101 in Example 1 in JP-A-2-854 was subjected tothe same tests in the same manner as in Example 1 in the above citedpatent application except that sodium thiosulfate to be used as fixingsolution was replaced by the compound of the present invention. Theresults were similar to that described above.

EXAMPLE 18

A light-sensitive material (direct positive color light-sensitivematerial) prepared in the same manner as in Specimen 1 in Example 1 inJP-A-2-90145 was subjected to the same tests in the same manner as inExample 1 in the above cited patent application except that ammoniumthiosulfate to be used as blix solution was replaced by the compound ofthe present invention. The results were similar to that described above.

EXAMPLE 19

A light-sensitive material (color reversal paper) prepared in the samemanner as in the color photographic light-sensitive material in Example2 in JP-A-1-158431 was subjected to the same tests in the same manner asin Example 2 in the above cited patent application except that ammoniumthiosulfate to be used as blix solution was replaced by the compound ofthe present invention. The results were similar to that described above.

Examples corresponding to the second embodiment of the present inventionwill be set forth hereinafter.

EXAMPLE 20

A multilayer color photographic paper was prepared in the same manner asin Example 5. The specimen was imagewise exposed to light, and thensubjected to processing in the same manner as in Example 5 except thatthe compound (fixing agent) to be incorporated in the blix solution asset forth in Table 3 was replaced by the compound set forth in Table 9.

After the running processing, the blix bath and the rinse bath 1 werevisually examined for the presence of precipitates.

The specimen was measured for magenta reflection density (Dmin) on theunexposed portion by means of an X-rite densitometer.

Another batch of the specimen was subjected to the same runningprocessing as mentioned above except that ferric ammoniumethylenediaminetetraacetate to be incorporated in the blix solution wasreplaced by ferric ammonium 1,3-propylenediaminetetraacetate. The blixbath and the rinse bath 1 were then visually examined for the presenceof precipitates. The specimen was measured for magenta reflectiondensity (Dmin) on the unexposed portion by means of an X-ritedensitometer. The results are set forth in Table 9. Table 9 shows thatthe use of the compound of the present invention as fixing agent instead of thiosulfate can provide excellent results, i.e., noprecipitation, excellent solution stability and low density (Dmin,bleach fog) on the unexposed portion. This tendency was remarkableparticularly when a bleaching agent having a high redox potential wasused as bleaching agent.

                                      TABLE 9                                     __________________________________________________________________________                  Magenta                                                                             Presence                                                                           Presence                                                           density                                                                             of pre-                                                                            of pre-                                                      Bleaching                                                                           (Dmin) on                                                                           cipitates                                                                          cipitates                                            Fixing  agent in                                                                            unexposed                                                                           in blix                                                                            in rinse                                             agent   blix bath                                                                           portion                                                                             bath bath 1                                               __________________________________________________________________________    Ammonium                                                                              1     0.15  B    C    Comparative                                     thiosulfate                                                                           2     0.18  D    D                                                    Compound B-1                                                                          1     0.11  A    A    Present                                                                       invention                                               2     0.10  A    A                                                    Compound B-15                                                                         1     0.11  A    A    Present                                                                       invention                                               2     0.11  A    A                                                    Compound B-30                                                                         1     0.11  A    A    Present                                                                       invention                                               2     0.11  A    A                                                    Compound B-40                                                                         1     0.12  A    A    Present                                                                       invention                                               2     0.11  A    A                                                    Compound B-64                                                                         1     0.11  A    A    Present                                                                       invention                                               2     0.10  A    A                                                    __________________________________________________________________________     <Evaluation of the presence of                                                A: No precipitates visually observed                                          B: A small amount of precipitates visually observed                           C: A large amount of precipitates visually observed                           D: An extremely large amount of precipitates visually observed                Note)                                                                         Bleaching agent 1: Ferric ammonium ethylenediaminetetraacetate                Bleaching agent 2: Ferric ammonium 1,3propylenediaminetetraacetate       

EXAMPLE 21

Tests were effected in the same manner as in Example 20 except thatCompound B-1 was replaced by Compounds B-5, B-23, B-41 and B-67,respectively.

As a result, excellent results were obtained, i.e., no precipitation andlittle bleach fog even upon running processing.

This tendency was particularly remarkable when a bleaching agent havinga high redox potential was used as bleaching agent.

EXAMPLE 22

Tests were effected in the same manner as in Example 1 except that theconcentration of the fixing agent (compound of the present invention) inthe blix bath was altered to 0.02, 0.08, 0.2, and 0.5 mol/l,respectively. The specimen was then measured for the amount of silverleft on the unexposed portion by X-ray fluorescence.

However, as bleaching agent there was used only ferric ammoniumethylenediaminetetraacetate.

The results are set forth in Table 10.

Table 10 shows that the use of the compound of the present invention inan amount of 0.2 mol/l or more can provide excellent results.

                                      TABLE 10                                    __________________________________________________________________________                  Residual                                                                Fixing                                                                              amount   Magenta Presence of                                            agent con-                                                                          of silver                                                                              density on                                                                            preci-                                                                              Presence of                                      centration                                                                          on unexposed                                                                           unexposed                                                                             pitates in                                                                          precipitates in                          Fixing agent                                                                          (mol/l)                                                                             portion (μg/cm.sup.2)                                                               portion (Dmin)                                                                        blix bath                                                                           Rinse bath 1                             __________________________________________________________________________    Ammonium                                                                              0.02  65       1.85    B     B (C)                                    thiosulfate                                                                           0.08  58       1.70    B     B (C)                                            0.20  1.8      0.30    B     C (C)                                            0.50  0.3      0.15    c     D (C)                                    Compound B-1                                                                          0.02  65       1.85    A     A (C)                                    0.08    59    1.75     A       A (C)                                                  0.20  1.4      0.11    A     A (P)                                            0.50  0.2      0.10    A     A (P)                                    Compound B-15                                                                         0.02  65       1.84    A     A (C)                                            0.08  61       1.77    A     A (C)                                            0.20  1.2      0.11    A     A (P)                                            0.50  0.3      0.11    A     A (P)                                    Compound B-30                                                                         0.02  65       1.85    A     A (C)                                            0.08  60       1.70    A     A (C)                                            0.20  1.5      0.11    A     A (P)                                            0.50  0.3      0.10    A     A (P)                                    __________________________________________________________________________     <Evaluation of the presence of                                                A: No precipitates visually observed                                          B: A small amount of precipitates visually observed                           C: A large amount of precipitates visually observed                           D: An extremely large amount of precipitates visually observed                Note)                                                                         P: Present invention                                                          C: Comparative                                                           

EXAMPLE 23

Tests were effected in the same manner as in Example 22 except thatCompound B-1 was replaced by Compounds B-5, B-23, B-41 and B-67,respectively.

As a result, it was found that the use of the compound of the presentinvention in an amount of 0.2 mol/l or more can provide excellentresults as in Example 22.

EXAMPLE 24

The light-sensitive material as prepared in Example 22 was imagewiseexposed to light, and then processed in the same manner as in Example 7except that the fixing agent to be incorporated in the blix solution wasreplaced by the compounds set forth in Table 11.

After the running processing, the blix bath and the rinse bath 1 werevisually examined for the presence of precipitates.

The specimen was measured for magenta reflection density (Dmin) on theunexposed portion by means of an X-rite densitometer.

Another batch of the specimen was subjected to the same runningprocessing as mentioned above except that ferric ammoniumethylenediaminetetraacetate to be incorporated in the blix solution wasreplaced by ferric ammonium 1,3-propylenediaminetetraacetate. The blixbath and the rinse bath 1 were then visually examined for the presenceof precipitates. The specimen was measured for magenta reflectiondensity (Dmin) on the unexposed portion by means of an X-raydensitometer. The results are set forth in Table 11. Table 11 shows thatthe use of the compound of the present invention as fixing agent instead of thiosulfate can provide excellent results, i.e., noprecipitation, excellent solution stability and low density (Dmin,bleach fog) on the unexposed portion. This tendency was remarkableparticularly when a bleaching agent having a high redox potential wasused as bleaching agent.

                                      TABLE 11                                    __________________________________________________________________________                  Magenta                                                                             Presence                                                                           Presence                                                           density                                                                             of pre-                                                                            of pre-                                                      Bleaching                                                                           (Dmin) on                                                                           cipitates                                                                          cipitates                                            Fixing  agent in                                                                            unexposed                                                                           in blix                                                                            in rinse                                             agent   blix bath                                                                           portion                                                                             bath bath 1                                               __________________________________________________________________________    Ammonium                                                                              1     0.17  B    C    Comparative                                     thiosulfate                                                                           2     0.20  D    D                                                    Compound B-1                                                                          1     0.12  A    A    Present                                                                       invention                                               2     0.11  A    A                                                    Compound B-15                                                                         1     0.12  A    A    Present                                                                       invention                                               2     0.12  A    A                                                    Compound B-30                                                                         1     0.12  A    A    Present                                                                       invention                                               2     0.12  A    A                                                    Compound B-40                                                                         1     0.13  A    A    Present                                                                       invention                                               2     0.12  A    A                                                    Compound B-64                                                                         1     0.12  A    A    Present                                                                       invention                                               2     0.11  A    A                                                    __________________________________________________________________________     <Evaluation of the presence of                                                A: No precipitates visually observed                                          B: A small amount of precipitates visually observed                           C: A large amount of precipitates visually observed                           D: An extremely large amount of precipitates visually observed                Note)                                                                         Bleaching agent 1: Ferric ammonium ethylenediaminetetraacetate                Bleaching agent 2: Ferric ammonium 1,3propylenediaminetetraacetate       

EXAMPLE 25

Tests were effected in the same manner as in Example 24 except thatCompound B-1 was replaced by Compounds B-5, B-23, B-41 and B-67,respectively.

As a result, excellent results were obtained, i.e., no precipitation andlittle bleach fog even upon running processing as in Example 24.

This tendency was particularly remarkable when a bleaching agent havinga high redox potential was used as bleaching agent.

EXAMPLE 26

A multilayer color photographic paper was prepared by coating variouslayers having the following compositions on a polyethylenedouble-laminated paper support which had been corona-discharged on thesurface thereof. The coating solutions for the various layers wereprepared as follows:

Preparation of 1st Layer Coating Solution

60.0 g of a yellow coupler (ExY) and 28.0 g of a discoloration inhibitor(Cpd-1) were dissolved in 150 cc of ethyl acetate, 1.0 cc of a solvent(Solv-3) and 3.0 cc of a solvent (Solv-4). The solution was added to 450cc of a 10% aqueous solution of sodium dodecylbenzenesulfonate. Themixture was then subjected to dispersion by means of an ultrasonichomogenizer. The dispersion was then mixed with 420 g of a silverchlorobromide emulsion containing a blue-sensitive sensitizing dye asset forth below (silver bromide content: 0.7 mol %) to prepare the 1stlayer coating solution.

Coating solutions for the 2nd layer to the 7th layer were prepared inthe same manner as mentioned above. As gelatin hardener for each ofthese layers there was used 1,2-bis(vinylsulfonyl)ethane.

As spectral sensitizing dyes for each of these layers there were usedthe following compounds:

Blue-sensitive emulsion layer:

Anhydro-5,5'-dichloro-3,3'-disulfoethylthiacyanine hydroxide

Green-sensitive emulsion layer:

Anhydro-9-ethyl-5,5'-diphenyl-3,3'-disulfoethyloxacarbocyanine hydroxide

Red-sensitive emulsion layer:

3,3'-Diethyl-5-methoxy-9,11-neopentylthiadicarbodianine iodide

As stabilizer for each of these layers there was used a 7:2:1 (molarratio) mixture of 1-(2-Acetoaminophenyl)- 5-mercaptotetrazole,1-phenyl-5-mercaptotetrazole and1-(p-methoxyphenyl)-5-mercaptotetrazole.

As irradiation-inhibiting dyes there were used the following compounds:

Disodium [3-carboxy-5-hydroxy-4-(3-(3-carboxy-5-oxo-1-(2,5-bisulfonatephenyl)-2-pyrazolin-4-ylidene)-1-propenyl)-1-pyrazolyl]benzene-2,5-disulfonate;

TetrasodiumN,N'-(4,8-dihydroxy-9,10-dioxo-3,7-disulfonateanthracene-1,5-diyl)bis(aminomethanesulfonate);

Disodium[3-cyano-5-hydroxy-4-(3-(3-cyano-5-oxo-1-(4-sulfonatephenyl)-2-pyrazolin-4-ylidene)-1-pentanyl)-1-pyrazolyl]benzene-4-sulfonate

Layer Structure

The composition of each layer will be set forth below. The figureindicates the coated amount of component (g/m²). The coated amount ofsilver halide emulsion is represented as calculated in terms of silver.

Support

Polyethylene double-laminated paper support which has beencorona-discharged on the surface thereof

    ______________________________________                                        1st layer: blue-sensitive layer                                               Above mentioned silver 0.29                                                   chlorobromide emulsion                                                        (AgBr content: 0.7 mol %; cubic;                                              average grain size: 0.9 μm)                                                Gelatin                1.80                                                   Yellow coupler (ExY)   0.60                                                   Discoloration inhibitor (Cpd-1)                                                                      0.28                                                   Solvent (Solv-3)       0.01                                                   Solvent (Solv-4)       0.03                                                   2nd layer: color stain inhibiting layer                                       Gelatin                0.80                                                   Color stain inhibitor (Cpd-2)                                                                        0.055                                                  Solvent (Solv-1)       0.03                                                   Solvent (Solv-2)       0.15                                                   3rd layer: green-sensitive layer                                              Above mentioned silver 0.18                                                   chlorobromide emulsion                                                        (AgBr content: 0.7 mol %; cubic;                                              average grain size: 0.45 μm)                                               Gelatin                1.86                                                   Magenta coupler (ExM)  0.27                                                   Discoloration inhibitor (Cpd-3)                                                                      0.17                                                   Discoloration inhibitor (Cpd-4)                                                                      0.10                                                   Solvent (Solv-1)       0.2                                                    Solvent (Solv-2)       0.03                                                   4th layer: color stain inhibiting layer                                       Gelatin                1.70                                                   Color stain inhibitor (Cpd-2)                                                                        0.065                                                  Ultraviolet absorbent (UV-1)                                                                         0.45                                                   Ultraviolet absorbent (UV-2)                                                                         0.23                                                   Solvent (Solv-1)       0.05                                                   Solvent (Solv-2)       0.05                                                   5th layer: red-sensitive layer                                                Above mentioned silver 0.21                                                   chlorobromide emulsion                                                        (AgBr content: 4 mol %; cubic;                                                average grain size: 0.5 μm)                                                Gelatin                1.80                                                   Cyan coupler (ExC-1)   0.26                                                   Cyan coupler (ExC-2)   0.12                                                   Discoloration inhibitor (Cpd-1)                                                                      0.20                                                   Solvent (Solv-1)       0.16                                                   Solvent (Solv-2)       0.09                                                   Color develoment accelerator                                                                         0.15                                                   (Cpd-5)                                                                       6th layer: ultraviolet absorbing layer                                        Gelatin                0.70                                                   Ultraviolet absorbent (UV-1)                                                                         0.26                                                   Ultraviolet absorbent (UV-2)                                                                         0.07                                                   Solvent (Solv-1)       0.30                                                   Solvent (Solv-2)       0.09                                                   7th layer: protective layer                                                   Gelatin                1.07                                                   ______________________________________                                    

Yellow Coupler (ExY)

α-Pivalyl-α-(3-benzyl-1-hydantoinyl)-2-chloro-5-[β-(dodecylsulfonyl)butylamide]acetanilide

Magenta Coupler (ExM)

7-Chloro-6-isopropyl-3-(3-[(2-butoxy-5-tert-octyl)benzenesulfonyl]propyl)-1H-pyrazolo[5,1-C]-1,2,4-triazole

Cyan Coupler (ExC-1)

2-Pentafluorobenzamide-4-chloro-5[2-(2,4-di-tert-amylphenoxy)-3-methylbutylamidephenol

Cyan Coupler (ExC-2)

2,4-Dichloro-3-methyl-6-[α-(2,4-di-tert-amylphenoxy)butylamide]phenol

Discoloration Inhibitor (Cpd-1) ##STR51## Color Stain Inhibitor (Cpd-2)2,5-Di-tert-octylhydroquinone

Discoloration Inhibitor (Cpd-3)

7,7'-Dihydroxy-4,4,4',4'-tetramethyl-2,2'-spirochroman

Discoloration Inhibitor (Cpd-4)

N-(4-dodecyloxyphenyl)-morpholine

Color Development Accelerator (Cpd-5)

p-(p-Toluenesulfonamide)phenyl dodecane

Solvent (Solv-1)

Di(2-ethylhexyl)phthalate

Solvent (Solv-2)

Dibutyl phthalate

Solvent (Solv-3)

Di(i-nonyl) phthalate

Solvent (Solv-4)

N,N-diethylcarbonamide-methoxy-2,4-di-t-amylbenzene

Ultraviolet Absorbent (UV-1)

2-(2-Hydroxy-3,5-di-tert-amylphenyl)benzotriazole

Ultraviolet Absorbent (UV-2)

2-(2-Hydroxy-3,5-di-tert-butylphenyl)benzotriazole

These specimens were subjected to black-and-white exposure by means of asensitometer (Type FWH, available from Fuji Photo Film Co., Ltd.).

These specimens were then subjected to the same tests as effected inExample 20 by means of a paper processing machine.

The results are set forth in Table 12.

Table 12 shows that the use of the compound of the present invention asfixing agent in stead of thiosulfate can provide excellent results,i.e., no precipitation, excellent solution stability and low density(Dmin, bleach fog) on the unexposed portion. This tendency wasremarkable particularly when a bleaching agent having a high redoxpotential was used as bleaching agent.

                                      TABLE 12                                    __________________________________________________________________________                  Magenta                                                                             Presence                                                                           Presence                                                           density                                                                             of pre-                                                                            of pre-                                                      Bleaching                                                                           (Dmin) on                                                                           cipitates                                                                          cipitates                                            Fixing  agent in                                                                            unexposed                                                                           in blix                                                                            in rinse                                             agent   blix bath                                                                           portion                                                                             bath bath 1                                               __________________________________________________________________________    Ammonium                                                                              1     0.16  B    C    Comparative                                     thiosulfate                                                                           2     0.20  D    D                                                    Compound B-1                                                                          1     0.13  A    A    Present                                                                       invention                                               2     0.11  A    A                                                    Compound B-12                                                                         1     0.14  A    A    Present                                                                       invention                                               2     0.12  A    A                                                    Compound B-30                                                                         1     0.13  A    A    Present                                                                       invention                                               2     0.12  A    A                                                    Compound B-65                                                                         1     0.14  A    A    Present                                                                       invention                                               2     0.12  A    A                                                    Compound B-68                                                                         1     0.13  A    A    Present                                                                       invention                                               2     0.12  A    A                                                    __________________________________________________________________________     <Evaluation of the presence of                                                A: No precipitates visually observed                                          B: A small amount of precipitates visually observed                           C: A large amount of precipitates visually observed                           D: An extremely large amount of precipitates visually observed                Note)                                                                         Bleaching agent 1: Ferric ammonium ethylenediaminetetraacetate                 Bleaching agent 2: Ferric ammonium 1,3propylenediaminetetraacetate      

EXAMPLE 27

Tests were effected in the same manner as in Example 26 except thatCompound B-1 was replaced by Compounds B-5, B-23, B-26 and B-49,respectively.

As a result, excellent results were obtained, i.e., no precipitation andlittle bleach fog even upon running processing as in Example 26.

This tendency was particularly remarkable when a bleaching agent havinga high redox potential was used as bleaching agent.

EXAMPLE 28

The same color light-sensitive material for picture taking as preparedin Specimen 201 in Example 2 in JP-A-2-90151 was imagewise exposed tolight, and then subjected to continuous processing (running test) in thefollowing steps until the replenishment reached twice the tank capacityof the blix bath.

    ______________________________________                                        Processing step                                                                                   Temper-  Replenish-                                                                            Tank                                     Step     Time       ature    ment rate*                                                                            capacity                                 ______________________________________                                        Color    3 min. 15 sec.                                                                           38.0° C.                                                                        23 ml   15 l                                     development                                                                   Blix     2 min. 30 sec.                                                                           38.0° C.                                                                        20 ml   5 l                                      Rinse 1  30 sec.    38.0° C.                                                                        --      3 l                                      Rinse 2  20 sec.    38.0° C.                                                                        34 ml   3 l                                      Stabilizing                                                                            20 sec.    38.0° C.                                                                        20 ml   3 l                                      Drying   1 min.     55.0° C.                                           ______________________________________                                         *Determined per 35mm wide and 1m long lightsensitive material            

The rinse was effected in a countercurrent process wherein water flowsbackward.

The amount of the developer brought over to the bleaching step, theamount of the bleaching solution brought over to the fixing step, andthe amount of the fixing solution brought over to the washing step were2.5 ml, 2.0 ml, and 2.0 ml per m of 35-mm wide light-sensitive material,respectively. The time for crossover was 5 seconds in all the steps.This crossover time is included in the processing time at the previousstep.

The various processing solutions had the following compositions:

    ______________________________________                                                         Running                                                                       Solution Replenisher                                         ______________________________________                                        Developer                                                                     Diethylenetriamine-                                                                              2.0    g       2.2  g                                      pentaacetic acid                                                              1-Hydroxyethylidene-                                                                             3.3    g       3.3  g                                      1,1-diphosphonic acid                                                         Sodium sulfite     3.9    g       5.2  g                                      Potassium carbonate                                                                              37.5   g       39.0 g                                      Potassium bromide  1.4    g       0.4  g                                      Potassium iodide   1.3    mg      --                                          Hydroxylamine sulfate                                                                            2.4    g       3.3  g                                      2-Methyl-4-[N-ethyl-N-                                                                           4.5    g       6.1  g                                      (β-hydroxyethyl)amino]                                                   aniline sulfate                                                               Water to make      1.0    l       1.0  l                                      pH                 10.05          10.15                                       Blix solution                                                                 Ammonium thiosulfate                                                                             280    ml      560  ml                                     (700 g/l)                                                                     or compound of the present                                                                       1.32   mol     2.64 mol                                    invention                                                                     Ammonium sulfite   40.0   g       80.0 g                                      Ferric ammonium 1,3-                                                                             144.0  g       288.0                                                                              g                                      propylenediaminetetra-                                                        acetate monohydrate                                                           Ammonium bromide   40.0   g       80.0 g                                      Ammonium nitrate   20.0   g       40.0 g                                      Water to make      1.0    l       1.0  l                                      pH at 25° C. adjusted with                                                                5.8    5.6                                                 acetic acid and aqueous ammonia                                               ______________________________________                                    

Washing Solution (The running solution was used also as replenisher)

Tap water was passed through a mixed bed column packed with an H-typestrongly acidic cation exchange resin (Amberlite IR-120B available fromRohm & Haas) and an OH-type strongly basic anion exchange resin(Amberlite IRA-400 available from the same company) so that the calciumand magnesium ion concentrations were each reduced to 3 mg/l or less.Dichlorinated sodium isocyanurate and sodium sulfate were then added tothe solution in amounts of 20 mg/l and 150 mg/l, respectively.

The washing solution thus obtained had a pH value of 6.5 to 7.5.

    ______________________________________                                        Stabilizing solution (The running solution was also used                      as replenisher)                                                               ______________________________________                                        37% Formalin               2.0 ml                                             Polyoxyethylene-p-monononylphenylether                                                                   0.3 g                                              (mean polymerization degree: 10)                                              Disodium ethylenediaminetetraacetate                                                                     0.05 g                                             Water to make              1.0 l                                              pH                         5.8-8.0                                            ______________________________________                                    

After the running processing, the blix bath and the rinse bath 1 werevisually examined for the presence of precipitates.

The specimen was measured for magenta transmission density (Dmin) on theunexposed portion by means of an X-ray densitometer. The results are setforth in Table 13.

Table 13 Shows that the use of the compound of the present invention asfixing agent in stead of thiosulfate can provide excellent results,i.e., no precipitation, excellent solution stability and low density(Dmin, bleach fog) on the unexposed portion even in the presence of ableaching agent having a high redox potential.

                  TABLE 13                                                        ______________________________________                                                  Magenta   Presence  Presence                                                  density   of pre-   of pre-                                                   (Dmin) on cipitates cipitates                                       Fixing    unexposed in blix   in rinse                                        agent     portion   bath      bath 1                                          ______________________________________                                        Ammonium  0.70      D         D      Compara-                                 thiosulfate                          tive                                     Compound B-1                                                                            0.59      A         A      Present                                                                       invention                                Compound B-15                                                                           0.60      A         A      Present                                                                       invention                                Compound B-30                                                                           0.61      A         A      Present                                                                       invention                                Compound B-40                                                                           0.60      A         A      Present                                                                       invention                                Compound B-64                                                                           0.61      A         A      Present                                                                       invention                                ______________________________________                                         <Evaluation of the presence of                                                A: No precipitates visually observed                                          B: A small amount of precipitates visually observed                           C: A large amount of precipitates visually observed                           D: An extremely large amount of precipitates visually observed           

EXAMPLE 29

Tests were effected in the same manner as in Example 28 except thatCompound B-1 was replaced by Compounds B-5, B-23, B-41 and B-67,respectively.

As a result, it was found that the use of the fixing agent of thepresent invention can provide excellent results as in Example 28.

EXAMPLE 30

Tests were effected in the same manner as in Example 28 except that theconcentration of the fixing agent (compound of the present invention) inthe blix bath was altered to 0.02, 0.08, 0.5, 1.2 and 1.5 mol/l,respectively. The specimen was then measured for the amount of silverleft on the unexposed portion by X-ray fluorescence.

However, as bleaching agent there was used only ferric ammoniumethylenediaminetetraacetate. The results are set forth in Table 14.

Table 14 shows that the use of the compound of the present invention inthe amount as specified herein can provide excellent results.

                                      TABLE 14                                    __________________________________________________________________________                  Residual                                                                Fixing                                                                              amount          Presence of                                             agent con-                                                                          of silver                                                                            Magenta  preci- Presence of                                      centration                                                                          on unexposed                                                                         density on                                                                             pitates in                                                                           precipitates in                          Fixing agent                                                                          (mol/l)                                                                             portion                                                                              unexposed portion                                                                      blix bath                                                                            Rinse bath 1                             __________________________________________________________________________    Ammonium                                                                              0.02  480    1.70     B      B (C)                                    thiosulfate                                                                           0.08  400    1.32     B      B (C)                                            0.50  5.4    0.72     C      C (C)                                            1.20  0.8    0.68     D      D (C)                                            1.50  0.6    0.68     D      D (C)                                    Compound B-1                                                                          0.02  485    1.65     A      A (C)                                            0.08  420    1.39     A      A (C)                                            0.50  4.2    0.62     A      A (P)                                            1.20  0.6    0.58     A      A (P)                                            1.50  0.5    0.57             (P)                                     Compound B-15                                                                         0.02  488    1.70     A      A (C)                                            0.08  430    1.43     A      A (C)                                            0.50  4.3    0.62     A      A (P)                                            1.20  0.6    0.58     A      A (P)                                            1.50  0.5    0.58             (P)                                     Compound B-30                                                                         0.02  480    1.72     A      A (C)                                            0.08  420    1.40     A      A (C)                                            0.50  4.5    0.63     A      A (P)                                            1.20  0.6    0.58     A      A (P)                                            1.50  0.5    0.58              (P)                                    __________________________________________________________________________     <Evaluation of the presence of                                                A: No precipitates visually observed                                          B: A small amount of precipitates visually observed                           C: A large amount of precipitates visually observed                           D: An extremely large amount of precipitates visually observed                Note)                                                                         P: Present invention                                                          C: Comparative                                                           

EXAMPLE 31

Tests were effected in the same manner as in Example 30 except thatCompound B-1 was replaced by Compounds B-5, B-23, B-41 and B-67,respectively.

As a result, it was found that the use of the compound of the presentinvention in the amount as specified herein can provide excellentresults as in Example 30.

INDUSTRIAL APPLICABILITY

In accordance with the present invention, the compound represented bythe general formula (I) or (II) can be used as fixing agent forprocessing color photographic light-sensitive materials, andblack-and-white light-sensitive materials to accomplish a processingmethod which provides little stain under heat and humidity conditionsand excellent desilvering (fixing) properties.

Further, the compound represented by the general formula (III) or (IV)can be used as fixing agent in the blix solution for processing colorphotographic paper in a concentration of 0.1 mol/l or more to accomplisha processing method which provides improvements in the stability of theblix solution (no precipitation due to sulfurization) and little bleachfog.

What is claimed is:
 1. A process for processing an imagewise exposedsilver halide photographic material comprising a support having thereonat least one light-sensitive silver halide emulsion layer, comprisingthe steps of developing in a developing bath, containing a developingagent and processing in a bath having a fixing ability, wherein the bathhaving a fixing ability contains as a fixing agent at least one compoundrepresented by formula (I): ##STR52## wherein X represents N or C--R₁ ;Y and Z each represents O, S, N, N--R₂ or C--R₃ ; U represents O, S orN--R₄ ; and A.sup.⊖ represents --O.sup.⊖, --S.sup.⊖ or --N.sup.⊖ R, inwhich R₁, R₂, R₃ and R₄ may be the same or different and each represents--T)_(n) R' (wherein T represents --S--, --O--, ##STR53## --SO₂ -- orcombinations thereof; and n represents 0 or 1); R, R' and R" may be thesame or different and each represents a hydrogen atom, an alkyl group, acycloalkyl group, an alkenyl group, an alkynyl group or a heterocyclicgroup, with the proviso that at least one of R, R' and R" is substitutedby a carboxylic acid or sulfonic acid group; and X and U, Y and Z, and Zand U may be ring-closed.
 2. The process of claim 1, wherein saidcompound represented by formula (I) is a compound represented by formula(II): ##STR54## wherein X' represents N or C--R₅ ; Y' represents O, S,N--R₆ or ##STR55## R₅, R₆, R₇, R₈, R₉ and R₁₀ may be the same ordifferent and each represents a substituted or unsubstituted C₁₋₆ alkylgroup; and R₅, R₆, R₇, R₈ and R₉ each may be a hydrogen atom, with theproviso that at least one of R₅, R₆, R₇, R₈, R₉ and R₁₀ is substitutedby at least one carboxylic acid group or sulfonic acid group.
 3. Theprocess of claim 1 or 2, wherein the amount of said compound representedby formula (I) or (II) is contained in the bath having a fixing abilityin the range of from 1×10⁻⁵ to 10 mol/l.
 4. The process of claim 1 or 2,wherein when the halogen composition of the silver halide emulsion inthe photographic material to be processed is AgBrI (iodide content≧2 mol%), said compound represented by formula (I) or (II) is contained in thebath having a fixing ability in the range of from 0.5 to 2 mol/l.
 5. Theprocess of claim 1 or 2, wherein when the halogen composition of thesilver halide emulsion in the photographic material to be processed isAgBr or AgBrCl having a high silver chloride content (AgCl content≧80mol %), said compound represented by formula (I) or (II) is contained inthe bath having a fixing ability in the range of from 0.1 to 1 mol/l. 6.The process of claim 1 or 2, wherein said bath having a fixing abilityis substantially free of thiosulfates.
 7. The process of claim 1 or 2,wherein said bath having a fixing ability is a fixing bath or a blixbath.
 8. A processing composition having a fixing ability for processinga silver halide photographic material containing at least one compoundrepresented by formula (I) as set forth in claim
 1. 9. The process ofclaim 1, wherein the silver halide photographic material is ablack-and-white silver halide photographic material, and said bathhaving a fixing ability is a fixing bath containing at least onecompound represented by formula (I) as a fixing agent.
 10. The processof claim 1, wherein said photographic material is a color photographicmaterial, said developing bath is a color developing bath containing acolor developing agent, and said process comprises desilvering followingthe developing step.
 11. The process of claim 10, wherein saiddesilvering comprises one of (i) bleaching in a bleaching bathcontaining a bleaching agent and fixing in a fixing bath containing atleast one compound represented by formula (I) as a fixing agent, and(ii) bleach-fixing in blix bath containing a bleaching agent and atleast one compound represented by formula (I) as a fixing agent.
 12. Aprocess for processing an imagewise exposed silver halide colorphotographic material comprising a support having thereon at least onelight-sensitive silver halide emulsion layer, comprising the steps ofsubjecting the material to color development in a color developing bathcontaining a color developing agent, and then subjecting the material toblix in a blix bath, wherein said blix bath contains bleaching agent andat least one mesoionic compound represented by formula (III) or (IV) asa fixing agent in an amount of from 2×10⁻¹ to 3 mol/l and said blix bathis substantially free of other fixing agents: ##STR56## wherein Mrepresents a 5-membered heterocyclic ring where the ring members of theheterocyclic ring are selected from the group consisting of carbon atom,nitrogen atom, oxygen atom, sulfur atom and selenium atom; and A₁.sup.⊖represents --O.sup.⊖, --S.sup.⊖ or --.sup.⊖ NR₁₁ in which R₁₁ representsan alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group,an aralkyl group, an aryl group or a heterocyclic group; ##STR57##wherein X₁ represents N or C--R₁₃ ; Y₁ represents O, S, N or N--R₁₄ ; Zrepresents N, N--R₁₅ or C--R₁₆ ; and R₁₂, R₁₃, R₁₄, R₁₅ and R₁₆ eachrepresents an alkyl group, a cycloalkyl group, an alkenyl group, analkynyl group, an aralkyl group, an aryl group, a heterocyclic group, anamino group, an acylamino group, a sulfonamide group, a ureide group, asulfamoylamino group, an acyl group, a thioacyl group, a carbamoyl groupor a thiocarbamoyl group, with the proviso that R₁₃ and R₁₆ each may bea hydrogen atom and R₁₂ and R₁₃, R₁₂ and R₁₅, R₁₂ and R₁₆, R₁₄ and R₁₅,and R₁₄ and R₁₆ may together form a ring.
 13. The process of claim 12,wherein said blix bath contains a bleaching agent having a redoxpotential of 150 mV or more.
 14. The process of claim 12, wherein the5-membered heterocyclic ring represented by M is selected from the groupconsisting of an imidazolium ring, a pyrazolium ring, an oxazolium ring,a thiazolium ring, a triazolium ring, a tetrazolium ring, athiadiazolium ring, an oxadiazolium ring, a thiatriazolium ring and anoxatriazolium ring.